Methods and apparatuses for production of carbon, carbide electrodes, and carbon compositions

ABSTRACT

Method comprising providing at least one solid carbide chemical compound and reducing a metal cation with use of the solid carbide chemical compound. A method comprising producing elemental carbon material from the oxidation of carbide in at least one carbide chemical compound (e.g., calcium carbide) in at least one anode of an electrochemical cell apparatus, such as a galvanic cell apparatus. The cathode can be a variety of metals such as zinc or tin. The reaction can be carried out at room temperature and normal pressure. An external voltage also can be applied, and different forms of carbon can be produced depending on the reactants used and voltage applied. For carrying out the method, an apparatus comprising at least one galvanic cell comprising: at least one anode comprising at least one carbide chemical compound, and at least one cathode. For carrying out the method and constructing the apparatus, an electrode structure comprising at least one carbide chemical compound, wherein the carbide chemical compound is a salt-like carbide; and at least one electronically conductive element different from the carbide. Carbon compositions of various forms are also prepared by the methods and apparatus and with use of the electrode structure. Large pieces of pure carbon can be produced. Post-reaction processing of the carbon can be carried out such as exfoliation.

RELATED APPLICATIONS

This application claims priority to U.S. provisional application Ser.No. 62/066,456 filed Oct. 21, 2014 and Ser. No. 62/174,760 filed Jun.12, 2015, which are each hereby incorporated by reference in theirentireties.

BACKGROUND

Carbon is a commercially essential element which in elemental form is amaterial both found in nature (e.g., coal) and is also made fromindustrial processes. Methods of making carbon are essential totraditional and advanced technology industries. Elemental carbon can befound in various forms and allotropes including, for example, amorphouscarbon, crystalline carbon, carbon black, graphite, and diamond. Otherforms of carbon include, for example, glassy carbon, diamond likecarbon, carbene, and carbyne. Nature also provides different forms ofcoal which is largely carbon. Carbon powder and carbon fibers are otherforms of carbon essential to industry.

Nanoscale forms of carbon are also known including fullerenes (includingC₆₀ and C₇₀ fullerenes), carbon nanotubes (both single walled andmulti-walled), graphene (single layered or multi-layered), and aerogels.Diamond can be made synthetically by high pressure/high temperatureroutes or by physical or chemical vapor deposition routes. Vapordeposition can produce microcrystalline or nanocrystalline diamond inthin film form. Nanoscale forms of carbon represent a critical aspect ofnewer and better devices ranging from the next generation ofminiaturized transistors to more efficient batteries. Large area formsof nanoscale forms of carbon such as thin diamond films and graphene arealso critical.

In general, carbon production is associated with arduous processconditions such as high temperature, high pressure, vacuum, and/or highenergy sources like plasma. Such conditions generate expense and areenergy-intensive. They also generally lack versatility (e.g., inabilityfor a single process to be altered to produce different allotropes ofcarbon, or different size scales of carbon).

For example, DE 1667532 Greiner (1971) describes what is said to be lowtemperature diamond production from an electrochemical system which caninclude use of carbide in the electrolyte with use of temperatures of600° C. to 1000° C. However, no data are provided.

Also, U.S. Pat. No. 4,738,759 (1988) describes an electrolysis processwherein calcium carbide can be subjected to electrolysis to formgraphite sponge at the anode. Temperatures are used such as 700° C. to1,000° C.

A Chen M. S. thesis, August 2002, Univ. N. Texas, describeselectrochemical deposition of films of amorphous carbon and diamond likecarbon (DLC). Electrochemical deposition was carried out using a lowtemperature (less than −40° C.) solution of acetylene in liquid ammonia.

Kulak, Electrochem. Comm., 5, 2003, 301-305 describes room temperatureelectrodeposition of very thin, porous film containing carbon (50-100 nmthick) from a solution of lithium acetylide. However, the microscopicimages of the film indicate a low quality material (FIG. 2) and much ofthe film is not carbon apparently.

US 2011/0290655 (Nishikiori; Toyota) describes a method forelectrochemically depositing carbon film on an anode substrate using amolten salt electrolyte bath comprising a carbide ion and applying a DCvoltage to deposit the carbon film. The bath temperature is 250° C. to800° C. The carbon film is said to be mainly amorphous carbon includinggraphite-like carbon according to x-ray diffraction.

Despite such advances, a need exists for better, commercially friendly,and environmentally friendly approaches to elemental carbon materialproduction. This includes elemental carbon material that has highelemental purity and also a commercially useful structure andmorphology. One also wants to be able to control the form and morphologyof the elemental carbon material. Inexpensive methods are also needed.

SUMMARY

Embodiments and aspects described and claimed herein include, forexample, methods of making, apparatuses for carrying out methods ofmaking, components used in the apparatuses for method of making, methodsof using, and compositions produced by the methods of making Devices andderivative compositions which comprise compositions of elemental carbonmaterials are also described and claimed herein.

For example, a first aspect is a method comprising providing at leastone solid carbide chemical compound and reducing a metal cation with useof the solid carbide chemical compound. In one embodiment, the carbidechemical compound has an electronic conductivity of at least 10⁻⁸ S/cm.In one embodiment, the carbide chemical compound is a salt-like carbide.In another embodiment, the carbide chemical compound is calcium carbideor aluminum carbide.

In another embodiment, elemental carbon material is formed. In anotherembodiment, elemental carbon material is formed which is more than 50%sp2 carbon. In another embodiment, elemental carbon material is formedwhich is more than 50% sp3 carbon. In another embodiment, elementalcarbon material is formed which is more than 90% carbon.

In another embodiment, the reducing is carried out at a temperature ofabout 15° C. to about 50° C. In another embodiment, the reducing iscarried out at a pressure of about 720 torr to about 800 torr. Inanother embodiment, the reducing is carried out at a temperature ofabout 15° C. to about 50° C. and at a pressure of about 720 torr toabout 800 torr.

In another embodiment, the cation is a zinc, tin, iron, copper, orsilver cation. In another embodiment, the cation is a zinc or tincation.

In another embodiment, the reducing is carried out in an electrochemicalcell with a cathode compartment comprising the metal cation and an anodecompartment comprising the solid carbide chemical compound.

In another embodiment, the reducing is carried out in a galvanic cellwith a cathode compartment comprising the metal cation and an anodecompartment comprising the solid carbide chemical compound. In anotherembodiment, the reducing is carried out in a galvanic cell with acathode compartment comprising the metal cation and an anode compartmentcomprising the solid carbide chemical compound, and the galvanic cellfurther comprises at least one external voltage source.

In another embodiment, the reducing is carried out in a galvanic cellwith a cathode compartment comprising the metal cation and an anodecompartment comprising the solid carbide chemical compound, and thegalvanic cell does not comprise at least one external voltage source.

In another embodiment, the reducing is carried out without contactbetween the metal cation and the solid carbide chemical compound. Inanother embodiment, the reducing is carried out with contact between themetal cation and the solid carbide chemical compound. In anotherembodiment, the reducing is carried out with contact between the metalcation and the solid carbide chemical compound, and the metal cation isdissolved in at least one organic solvent.

In addition, a second aspect provides for a method comprising: producingelemental carbon material from the oxidation of carbide in at least onecarbide chemical compound in at least one anode of an electrochemicalcell apparatus. More particularly, a method is providing comprising:producing elemental carbon material from the oxidation of carbide in atleast one carbide chemical compound in at least one anode of a galvaniccell apparatus

In one embodiment, the electrochemical cell apparatus is a galvanic cellapparatus or an electrolytic cell apparatus. In another embodiment, theelectrochemical cell apparatus is a galvanic cell apparatus.

In another embodiment, the carbide chemical compound is a salt-likecarbide or an intermediate transition metal carbide. In anotherembodiment, the carbide chemical compound is a salt-like carbide. Inanother embodiment, the carbide chemical compound is a methanide, anacetylide, or a sesquicarbide. In another embodiment, the carbidechemical compound is calcium carbide, aluminum carbide, sodium carbide,magnesium carbide, lithium carbide, beryllium carbide, iron carbide,copper carbide, and chromium carbide. In another embodiment, the carbidechemical compound is calcium carbide or aluminum carbide. In anotherembodiment, the carbide chemical compound has sufficient electronicconductivity to function as an anode. In another embodiment, the carbidechemical compound has an electronic conductivity of at least 10⁻⁸ S/cm.

In another embodiment, the electrochemical cell apparatus furthercomprises at least one cathode. In another embodiment, theelectrochemical cell apparatus further comprises at least one cathodewhich is a metal cathode. In another embodiment, the electrochemicalcell apparatus further comprises at least one metal cathode, wherein thecathode is a zinc, tin, iron, copper, or silver cathode. In anotherembodiment, the electrochemical cell apparatus further comprises atleast one metal cathode, wherein the cathode is a zinc or tin cathode.

In another embodiment, the electrochemical cell apparatus anode iscontacted with at least one first solution comprising at least onesolvent and at least one salt and a galvanic cell apparatus cathode isalso contacted with at least one solution comprising at least onesolvent and at least one salt.

In another embodiment, the electrochemical cell apparatus furthercomprises at least one salt bridge. In another embodiment, theelectrochemical cell apparatus further comprises at least one ionexchange membrane.

In another embodiment, the reaction temperature for producing theelemental carbon material is about 10° C. to about 90° C. In anotherembodiment, the reaction temperature for producing the elemental carbonmaterial is about 15° C. to about 50° C. In another embodiment, thereaction temperature for producing the elemental carbon material isabout room temperature. In another embodiment, the reaction pressure forproducing the elemental carbon material is about 0.1 torr to about 5atmospheres. In another embodiment, the reaction pressure for producingthe elemental carbon material is about 720 torr to about 800 torr. Inanother embodiment, the elemental carbon material is produced at aboutnormal pressure.

In another embodiment, the production of elemental carbon material iscarried out without use of an external voltage source. In anotherembodiment, the electrochemical cell apparatus comprises an externalvoltage source to regulate the oxidation reaction. In anotherembodiment, the production of carbon is carried out with use of anexternal voltage source to regulate the oxidation reaction. In anotherembodiment, the production of carbon is carried out with use of anexternal voltage source to regulate the oxidation reaction, and anexternal voltage is used at a particular voltage to enhance productionof one elemental carbon material product over other different elementalcarbon products.

In another embodiment, the elemental carbon material is more than 50%sp2 carbon. In another embodiment, the elemental carbon material is morethan 50% sp3 carbon. In another embodiment, the elemental carbonmaterial is more than 90% carbon.

In another embodiment, the elemental carbon material comprisestwo-dimensional plate-like structures. In another embodiment, theelemental carbon material comprises two-dimensional plate-likestructures stacked on top of one another. In another embodiment, theelemental carbon material comprises at least some three-dimensionalstructures. In another embodiment, the elemental carbon materialcomprises at least some pieces which have a lateral dimension of atleast one mm.

In another embodiment, the elemental carbon material is subjected to atleast one purification step. In another embodiment, the elemental carbonmaterial is treated with acid and water. In another embodiment, theelemental carbon material is subjected to at least one step whichproduces particles of the elemental carbon material. In anotherembodiment, the elemental carbon material is subjected to at least oneexfoliation step to produce graphene.

In another embodiment, the electrochemical cell apparatus is a galvaniccell apparatus which produces electrical power to power at least oneload which is another electrochemical cell.

In another embodiment, the electrochemical cell apparatus is a galvaniccell apparatus, the carbide chemical compound is calcium carbide oraluminum carbide, wherein the galvanic cell apparatus anode is contactedwith a solution comprising at least one organic solvent and at least onedissolved salt, and the galvanic cell apparatus cathode is alsocontacted with a solution comprising at least one organic solvent and atleast one dissolved salt, and wherein the elemental carbon material isproduced at about 15° C. to about 50° C. and about 720 torr to about 800torr.

Another aspect provides for an apparatus comprising at least oneelectrochemical cell apparatus comprising: at least one anode comprisingat least one carbide chemical compound, and at least one cathode. Moreparticularly, an apparatus is provided comprising at least one galvaniccell apparatus comprising: at least one anode comprising at least onecarbide chemical compound, and at least one cathode. In one embodiment,the electrochemical cell apparatus is a galvanic cell apparatus or anelectrolytic cell apparatus. In another embodiment, the electrochemicalcell apparatus is a galvanic cell apparatus.

In another embodiment, the carbide chemical compound is a salt-likecarbide or an intermediate transition metal carbide. In anotherembodiment, the carbide chemical compound is a salt-like carbide. Inanother embodiment, the carbide chemical compound is calcium carbide oraluminum carbide. In another embodiment, the carbide chemical compoundhas sufficient electronic conductivity to function as an anode. Inanother embodiment, the carbide chemical compound has an electronicconductivity of at least 10⁻⁸ S/cm. In another embodiment, the carbidechemical compound is in the form of individual pieces or particles. Inanother embodiment, the carbide chemical compound is in the form ofindividual pieces or particles having a size of less than one cm. Inanother embodiment, the carbide chemical compound contacts at least oneelectrically conductive material. In another embodiment, the carbidechemical compound is held in an electrically conductive container.

In another embodiment, the electrochemical cell apparatus anode iscontacted with a solution comprising at least one organic solvent and atleast one dissolved salt. In another embodiment, the electrochemicalcell apparatus cathode is contacted with a solution comprising at leastone organic solvent and at least one dissolved salt. In anotherembodiment, the electrochemical cell apparatus cathode is a metalcathode. In another embodiment, the electrochemical cell apparatuscomprises at least one salt bridge or at least one ion exchangemembrane. In another embodiment, the electrochemical cell apparatuscomprises an external voltage source to regulate an oxidation reactionof carbide in the carbide chemical compound. In another embodiment, theapparatus further comprises at least one solution comprising at leastone solvent and at least one dissolved salt, and the solution is free ofdissolved carbide chemical compound.

In another embodiment, an electrochemical cell apparatus is provided forcarrying out the methods described herein. In particular, a galvaniccell apparatus is provided for carrying out the methods describedherein.

In another embodiment, the anode is an anode electrode structurecomprising at least one carbide chemical compound, wherein optionallythe carbide chemical compound is a salt-like carbide; and at least oneelectronically conductive structural element different from the carbidechemical compound and contacting the at least one carbide chemicalcompound.

Still further, another aspect provides for an electrode structurecomprising at least one carbide chemical compound, wherein optionallythe carbide chemical compound is a salt-like carbide; and at least oneelectronically conductive structural element different from the carbidechemical compound and contacting the at least one carbide chemicalcompound. The electrode structure can be a solid electrode structure;also, the electrode structure can be adapted to function as an anode.

In one embodiment, the carbide chemical compound is methanide,acetylide, or sesquicarbide. In another embodiment, the carbide chemicalcompound is calcium carbide, aluminum carbide, sodium carbide, magnesiumcarbide, lithium carbide, or beryllium carbide. In another embodiment,the carbide chemical compound is calcium carbide or aluminum carbide. Inanother embodiment, the carbide chemical compound has sufficientelectronic conductivity to function as an anode. In another embodiment,the carbide chemical compound has an electronic conductivity of at least10⁻⁸ S/cm. In another embodiment, the carbide chemical compound is inthe form of individual pieces or particles. In another embodiment, thecarbide chemical compound is in the form of individual pieces orparticles having a size of less than one cm. In another embodiment, thecarbide chemical compound is in the form of individual pieces orparticles having a size of at least one micron. In another embodiment,the carbide chemical compound is divided into separate portions whichare each contacted with at least one electrically conductive structuralelement. In another embodiment, the carbide chemical compound is atleast about 95% pure.

In another embodiment, the electronically conductive structural elementis a binder for the carbide chemical compound. In another embodiment,the electronically conductive structural element is a container and thecarbide chemical compound is held in the container. In anotherembodiment, the electronically conductive structural element is acontainer and the carbide chemical compound is held in the container,and the container has openings which allow fluid to enter the containerand contact the carbide chemical compound. In another embodiment, theelectronically conductive structural element is a metallic container andthe carbide chemical compound is held in the metallic container. Inanother embodiment, the electronically conductive structural elementcomprises at least one conductive rod. In another embodiment, theelectrode structure is adapted to be removably attached to an apparatus.In another embodiment, the electronically conductive structural elementof the electrode structure comprises at least one current collector. Inanother embodiment, the electrode structure is adapted for use as ananode in an electrochemical cell apparatus for production of anelemental carbon material. In another embodiment, the electrodestructure is adapted for use as an anode in a galvanic cell apparatusfor production of elemental carbon material.

Another aspect provides for a method comprising operating at least oneanode in an electrochemical cell, wherein the anode comprises at leastcarbide chemical compound.

In one embodiment, the anode consists essentially of at least onecarbide chemical compound. In another embodiment, the anode consists ofat least one carbide chemical compound. In another embodiment, the anodeis part of an anode structure which further comprises at least oneelectronically conductive structural element different from the carbidechemical compound and contacting the at least one carbide chemicalcompound. In another embodiment, the anode is part of an anode structurewhich further comprises at least one metallic structural elementdifferent from the carbide chemical compound and contacting the at leastone carbide chemical compound. In another embodiment, the carbidechemical compound has sufficient electronic conductivity to function asan anode. In another embodiment, the carbide chemical compound has anelectronic conductivity of at least 10⁻⁸ S/cm. In another embodiment,the carbide chemical compound is a salt-like carbide. In anotherembodiment, the carbide chemical compound is calcium carbide or aluminumcarbide. In another embodiment, the electrochemical cell is a galvaniccell.

Another aspect is for a method comprising: producing elemental carbonmaterial from the oxidation of carbide in at least one carbide chemicalcompound which is in contact with a solution comprising at least oneorganic solvent and at least one dissolved salt comprising at least onemetal cation which is reduced.

In one embodiment, the reaction temperature for producing the elementalcarbon material is about 10° C. to about 90° C. In another embodiment,the reaction temperature for producing the elemental carbon material isabout 15° C. to about 50° C. In another embodiment, the reactiontemperature for producing the elemental carbon material is about roomtemperature. In another embodiment, the reaction pressure for producingthe elemental carbon material is about 0.1 torr to about 5 atmospheres.In another embodiment, the reaction pressure for producing the elementalcarbon material is about 720 torr to about 800 torr.

In another embodiment, the carbide chemical compound is a salt-likecarbide or an intermediate transition metal carbide. In anotherembodiment, the carbide chemical compound is a salt-like carbide. Inanother embodiment, the carbide chemical compound is a methanide, anacetylide, or a sesquicarbide. In another embodiment, the carbidechemical compound is calcium carbide or aluminum carbide.

Another aspect provides for an elemental carbon material composition (i)prepared by the methods described and/or claimed herein; and/or (ii)characterized as described and/or claimed herein. The elemental carbonmaterial can be in an unpurified form, a partially purified form, apurified form, a processed form, a doped form, and/or a reacted form.

In one embodiment, the elemental carbon material is more than 50% sp2carbon. In another embodiment, the elemental carbon material is morethan 50% sp3 carbon. In another embodiment, the elemental carbonmaterial is more than 90% carbon.

In another embodiment, the elemental carbon material comprisestwo-dimensional plate-like structures. In another embodiment, theelemental carbon material comprises two-dimensional plate-likestructures stacked on top of one another. In another embodiment, theelemental carbon material comprises graphene structures. In anotherembodiment, the elemental carbon material comprises graphite structures.In another embodiment, wherein the elemental carbon material comprisesthree-dimensional structures. In another embodiment, the elementalcarbon material comprises diamond. In another embodiment, the elementalcarbon material comprises diamond structures and/or diamond-likestructures. In another embodiment, the elemental carbon materialcomprises at least one piece which has a lateral dimension of at leastone mm, at least one cm. In another embodiment, the elemental carbonmaterial comprises at least one piece which has a volume of at least onecubic mm, or at least one cubic cm.

Also provided herein are one or more composition comprising theelemental carbon material compositions described herein. For example,the elemental carbon material can be mixed with one or more differentingredients.

Also provided herein are one or more devices, apparatuses, or systemscomprising the compositions described herein such as, for example, abattery device, an electronic device, or a filtration device. Otherembodiments include making and using such devices, apparatuses, andsystems.

At least some advantages for at least some embodiments described and/orclaimed herein include, for example, (i) an ambient temperature and/or anormal pressure reaction process to form high purity elemental carbonmaterials of very high carbon content; (ii) cost-effectiveness; (iii)environmental friendliness; and/or (iv) ability to control the nature ofthe elemental carbon material product in versatile ways.

More particularly, one of the most important advantages for at leastsome of the embodiments is the ability to produce an array of differentelemental carbon material reaction products in different forms.Therefore, the technology can yield numerous processes with many valueadded end products. Also, because of the physical states when thereaction occurs (the liquid state and solid state), one can enable theproduction of the various allotropes of elemental carbon material at ahigher quality level than any of the competing elemental carbonproduction technologies.

Another major advantage for at least some embodiments is scalability.For example, the electrochemical and galvanic reaction mechanism foroxidizing carbides to various allotropes and forms of elemental carbonmaterials is very scalable, meaning that the technology can be increasedin size without any major re-designs. Typically, the main obstacles withincreasing the scale of a process are physical limitations of theequipment at extreme conditions and gradients (e.g., temperature,concentration, etc.) within larger equipment as the scale increases.However, in most embodiments presently described and claimed, there areno extreme conditions in these processes. For example, preferably, theprocess is operated at or near room temperature and atmospheric pressureso there is little concern about the limitations of the equipment atextreme conditions as size is increased. Still other advantages aredescribed and evident in this application.

BRIEF DESCRIPTION OF THE FIGURES

The figures provide more description for representative embodimentsincluding many working examples.

FIG. 1 is a chart that provides the enthalpies of formation for variousallotropes of carbon.

FIG. 2 is a schematic diagram of a representative electrochemical (here,galvanic) system according to an embodiment of the invention.

FIG. 3 is a diagram of a representative electrochemical (here, galvanic)system according to an embodiment of the invention showing a directcurrent (DC) source and a variable resistor (i.e., example of externalvoltage source).

FIG. 4 shows a schematic drawing of the apparatus wherein an ionexchange membrane is below the two cells.

FIG. 5 shows a schematic drawing of the apparatus in which an ionexchange membrane is used and also a reference electrode (Ag/AgCl) isused.

FIG. 6 shows SEM data for elemental carbon material prepared by acomparative thermal method (U.S. application Ser. No. 14/213,533 and PCTApplication PCT/US2014/028755; scale bar 200 microns). One relativelylarger piece is evident.

FIG. 7 shows additional SEM data for elemental carbon material preparedby a comparative thermal method ((U.S. application Ser. No. 14/213,533and PCT Application PCT/US2014/028755; scale bar 200 microns).

FIG. 8 is a Scanning Electron Microscope (SEM) image showing elementalcarbon material reaction product on a bulk material scale (Example 1;zinc). The scale bar is 50 microns.

FIG. 9 is an SEM image showing the plate-like structures found in theelemental carbon material reaction product (Example 1; zinc). The scalebar is five microns.

FIG. 10 is an SEM image showing the plate-like structures found in theelemental carbon material reaction product (Example 1; zinc). The scalebar is two microns.

FIG. 11 is an SEM image showing the plate-like structures found in theelemental carbon material reaction product (Example 1; zinc). The scalebar is five microns.

FIG. 12 is an SEM image showing carbon reaction product on a bulkmaterial scale (Example 2; tin). The scale bar is 100 microns.

FIG. 13 is an SEM image showing the elemental carbon material reactionproduct (Example 2; tin). The scale bar is 20 microns.

FIG. 14 is an SEM image showing the three-dimensional crystals ofelemental carbon material (Example 2; tin). The scale bar is tenmicrons.

FIG. 15 is an SEM image showing a three-dimensional elemental carbonmaterial particle (Example 2; tin). The scale bar is 10 microns.

FIG. 16 is an SEM image showing the top region of the three-dimensionalelemental carbon material particle (Example 2; tin). The scale bar is 3microns.

FIG. 17 is schematic depiction of a representative, relatively smallerbench-scale sized electrochemical system (Examples 1 and 2).

FIG. 18 is a schematic depiction of a modified laboratory-scaleapparatus similar to the apparatus of FIG. 17 but adapted with an ionexchange membrane.

FIG. 19 is a diagram of a representative, relatively larger bench-scalesized electrochemical system compared to that of FIGS. 17 and 18(Examples 3 and 4).

FIG. 20 is a schematic depiction of a representative larger bench-scalesized electrochemical system showing the two cells (Examples 3 and 4).

FIG. 21 is a schematic depiction of a representative carbide cellaccording to an embodiment of the invention (Examples 3 and 4).

FIG. 22 is a schematic depiction of a representative zinc cell accordingto an embodiment of the invention (Examples 3 and 4).

FIG. 23 is a schematic depiction of a representative salt bridgeconnecting the carbide and zinc cells according to an embodiment of theinvention (Examples 3 and 4).

FIG. 24 shows SEM data for the elemental carbon material prepared inExample 3 (scale bar 10 microns).

FIG. 25 shows SEM data for the elemental carbon material prepared inExample 3 (scale bar 20 microns).

FIG. 26 shows SEM data for the elemental carbon material prepared inExample 3 (scale bar 50 microns).

FIG. 27 shows Raman spectral data (eight traces) for the elementalcarbon material prepared in Example 3.

FIG. 28 shows SEM data for the elemental carbon material prepared inExample 4 (scale bar 20 microns).

FIG. 29 shows additional SEM data for the elemental carbon materialprepared in Example 4 (scale bar 20 microns).

FIG. 30 shows EDAX data for the elemental carbon material prepared inExample 4.

FIG. 31 shows Raman spectral data for the elemental carbon materialprepared in Example 4.

FIG. 32 is an SEM image showing more of the elemental carbon material ofExample 4 (scale bar, 50 microns).

FIG. 33 shows a comparison for a large piece of elemental carbonmaterial from Example 5 (33 left) with a commercial graphene producthaving relatively smaller pieces (33 right), each with a 200 micronscale bar.

FIG. 34 is an SEM image showing a top view of a large piece of carbonproduct (Example 5, Sample C) (scale bar, 200 microns).

FIG. 35 is an SEM image showing Sample C with a perspective view(Example 5, scale bar, 200 microns).

FIG. 36 is a Raman spectrum (four traces) for Sample C (Example 5).

FIG. 37 is an SEM image showing Sample C (Example 5) and materialmorphology within crevices (scale bar, 40 microns).

FIG. 38 shows a schematic depiction for top view of Sample C (Example 5,scale bar, 390 microns).

FIG. 39 shows a schematic depiction for perspective view of edge ofSample C (Example 5, scale bar, 240 microns).

FIG. 40 is an SEM image showing Sample C (Example 5, scale bar, 30microns).

FIG. 41 is an SEM image showing Sample C, for an enlarged view of FIG.40 (scale bar, 5 microns).

FIG. 42 shows a comparison for elemental carbon material prepared by acomparative thermal method (42 left; U.S. application Ser. No.14/213,533 and PCT Application PCT/US2014/028755) with a large piece ofelemental carbon material prepared in Example 5 (42 right), each withscale bar of 200 microns.

FIG. 43 shows a comparison for elemental carbon material prepared by acomparative thermal method (43 left; U.S. application Ser. No.14/213,533 and PCT Application PCT/US2014/028755) with a large piece ofelemental carbon material prepared in Example 5 (43 right), each withscale bar of 30 microns.

FIG. 44 shows a comparison for elemental carbon material prepared by acomparative thermal method (44 left; U.S. application Ser. No.14/213,533 and PCT Application PCT/US2014/028755) with a large piece ofelemental carbon material prepared in Example 5 (44 right), each withscale bar of 5 microns.

FIG. 45 shows a comparison for Raman spectra for elemental carbonmaterial prepared by a comparative thermal method (45 left, U.S.application Ser. No. 14/213,533 and PCT ApplicationPCT/US2014/02875545A) with Raman spectra for a large piece of elementalcarbon material prepared in Example 5 (45 right).

FIG. 46 is a first SEM image showing the elemental carbon materialproduct in Example 6 with use of a potentiostat, Sample D (scale bar 10microns).

FIG. 47 is an SEM image showing the elemental carbon material product inExample 6 with use of a potentiostat, Sample D (scale bar 5 microns).

FIG. 48 is an SEM image showing the elemental carbon material product inExample 6 with use of a potentiostat, Sample D (scale bar 50 microns).

FIG. 49 shows two SEM images showing the elemental carbon materialproduct in Example 6 with use of a potentiostat, Sample D (49 left,scale bar 50 microns; 49 right, scale bar 10 microns).

FIG. 50 shows two SEM images showing the elemental carbon materialproduct in Example 6 with use of a potentiostat, Sample D (50 left,scale bar 10 microns; 50 right, scale bar 10 microns).

FIG. 51 is an SEM image showing the elemental carbon material product inExample 6 with use of a potentiostat, Sample D (scale bar 10 microns).

FIG. 52 shows SEM data for the elemental carbon material prepared inExample 6 (scale bar 100 microns).

FIG. 53 shows SEM data for the elemental carbon material prepared inExample 6 (scale bar 30 microns).

FIG. 54 shows SEM data for the elemental carbon material prepared inExample 6 (scale bar 10 microns).

FIG. 55 shows SEM data for the elemental carbon material prepared inExample 6 (scale bar 100 microns).

FIG. 56 shows SEM data for the elemental carbon material prepared inExample 6 (scale bar 20 microns).

FIG. 57 shows Raman spectral data (seven traces) for the elementalcarbon material prepared in Example 6.

FIG. 58 shows SEM data for the elemental carbon material prepared inExample 8 (scale bar, 50 microns).

FIG. 59 shows SEM data for the elemental carbon material prepared inExample 8 (scale bar, 10 microns).

FIG. 60 shows Raman spectral data for elemental carbon material preparedin Example 8.

FIG. 61 shows SEM data for the elemental carbon material prepared inExample 9 (scale bar, 5 microns).

FIG. 62 shows SEM data for the elemental carbon material prepared inExample 9 (scale bar, 10 microns).

FIG. 63 shows Raman spectral data for elemental carbon material preparedin Example 9.

FIG. 64 shows SEM data for the elemental carbon material prepared inExample 10 (scale bar, 200 microns).

FIG. 65 shows SEM data for the elemental carbon material prepared inExample 10 (scale bar, 30 microns).

FIG. 66 shows SEM data for the elemental carbon material prepared inExample 10 (scale bar, 10 microns).

FIG. 67 shows Raman spectra for Example 10.

FIG. 68 shows SEM data for the elemental carbon material prepared inExample 11 (scale bar, 10 microns).

FIG. 69 shows SEM data for the elemental carbon material prepared inExample 11 (scale bar, 40 microns).

FIG. 70 shows SEM data for the elemental carbon material prepared inExample 11 (scale bar, 30 microns).

FIG. 71 shows Raman spectral data for elemental carbon material preparedin Example 11.

DETAILED DESCRIPTION I. Introduction

The various aspects and claims summarized above and claimed below aredescribed in more detail hereinafter including with use of workingexamples.

References cited herein are incorporated by reference.

Priority U.S. provisional application Ser. No. 62/066,456 filed Oct. 21,2014 and Ser. No. 62/174,760 filed Jun. 12, 2015 are each herebyincorporated by reference in their entireties including their summaries,detailed descriptions, working examples, and figures.

U.S. application Ser. No. 14/213,533, filed Mar. 14, 2014 and publishedas 2014/0271441, describes a method of making carbon from carbide andmolten, metal salts in a thermal process but at relatively lowtemperature compared to prior art processes. PCT ApplicationPCT/US2014/028755, filed Mar. 14, 2014 and published as WO 2014/144374,also describes a method of making carbon from carbide and molten, metalsalts in a thermal process but at a relatively low temperature. Alsodescribed are processing steps to purify and treat the elemental carbonmaterial. FIGS. 6 and 7 show examples of elemental carbon materialsprepared by these methods.

In addition, the claim transitions “comprising,” “consisting essentiallyof,” and “consisting of” can be used to describe and/or claim thevarious embodiments described herein. Basic and novel features of theinvention are described herein.

In a nutshell, embodiments for the present inventions provide for, amongother things, methods of reacting carbides to produce elemental carbonmaterial and carbon allotropes.

In some embodiments of the present inventions, a voltage is varied,changed, or altered in a cell in which one of the cells contains acarbide electrode to change the nature of the elemental carbon materialsformed by the oxidation of carbide anions. Voltage may be varied,changed, or altered in a cell in which one of the cells is a carbide tochange the nature of the carbon materials formed by the oxidation ofacetylide anions, methanide anions, and/or sesquicarbide anions. In someembodiments, the carbon allotropes produced by the process arecontrolled by controlling the voltage between the cells in which one ofthe cells is a carbide.

For more background to the presently claimed inventions, FIG. 1 is achart that provides the enthalpies of formation for forms and allotropesof carbon prepared from a carbide reactant. FIG. 1 provides theassociated heats of formation DH_((formation)) in descending order withthe lower the DH_((formation)) value the more stable the state ofcarbon, with graphite being in the most stable state. The sources forFIG. 1 are an NIST webbook, the textbook Elements of Physical Chemistry(Peter Atkins), and Cherkasov, Nikolay B. et al., Carbon, vol. 36, p.324-329.

II. Methods of Production

A first aspect for a method of making is a method comprising providingat least one solid carbide chemical compound and reducing a metal cationwith use of the solid carbide chemical compound. The reducing can resultfrom a spontaneous, galvanic reaction, optionally with application of anexternal voltage. Alternatively, the reducing can be carried out with anon-spontaneous reaction with application of an external voltage.

A second aspect for a method of making provides for a method comprising:producing elemental carbon material from the oxidation of carbide in atleast one carbide chemical compound in at least one anode of anelectrochemical cell apparatus. Apparatuses which can used to carry outthis method are described further in, for example, Part III of thisapplication (see also, for example, Schematics in FIGS. 2-5 and 19).Also, carbide electrode structures which can be used to carry out thismethod are described further in, for example, Part IV of thisapplication (including methods of using carbide electrodes).

Still further, a third aspect for a method of making is for a methodcomprising: producing elemental carbon material from the oxidation ofcarbide in at least one carbide chemical compound which is in contactwith a solution comprising at least one organic solvent and at least onedissolved salt comprising at least one metal cation which is reduced.

Finally, elemental carbon material reaction products which can be formedfrom these methods are described further in Part V of this application.

The method of making can be based on a electrochemical cell apparatuswhich can be galvanic (spontaneous reaction) or electrolytic(non-spontaneous reaction). Preferably, the method makes use of agalvanic reaction using a galvanic cell apparatus. Preferably, thereaction is a spontaneous redox reaction. A galvanic reaction isgenerally known in the art as a spontaneous redox reaction wherein onemoiety is oxidized and another moiety is reduced. The moieties areconnected electrically to allow current to flow and the redox reactionto occur. A multimeter can be used to measure voltage and current flowfor such a reaction. No external electrical potential is needed toinduce the spontaneous reaction in a galvanic reaction. However, anexternal electrical potential can be used to control or modify thegalvanic reaction, while the reaction is still called a “galvanicreaction” or a “spontaneous reaction.” The discharge of the current flowcan be regulated. The galvanic reaction can be a source of power,voltage, and current, and these reactions can be used to power othersystems and loads as known in the art.

The elements of a method using a galvanic reaction are known anddescribed more hereinbelow. They include, for example, at least oneanode, at least one cathode, and connections between the anode andcathode to allow current flow and form a circuit. The connections canprovide electronic or ionic current flow. For example, wiring can beused and devices can be used to measure the potential and current flow.Ionic flow can be enabled with use of salt bridges or ion exchangemembranes. The salt bridge or ion exchange membrane can have a geometryand length which help to determine the rate of the redox reaction. Thetransport of the appropriately charged moiety, an anion, can be mediatedthrough the salt bridge or the ion exchange membrane to complete thecircuit. For instance, in one embodiment, a cation such as a zinc cationdissolved in the solution in the metal cell cannot migrate or transferthrough the ion exchange membrane. However the anion (e.g., Cl—) is ableto diffuse through the membrane and into the carbide cell. In oneembodiment, the salt bridge is replaced with, or used with, or comprisesan ion exchange membrane. In any event, the salt bridge or ion exchangemembrane can be adapted to avoid being a rate limiting step (“bottleneck”) for the process and pass as much charge as possible.

The elements of a method using an electrolytic reaction are also known.

In one embodiment, the electrochemical cell (e.g., galvanic cell)apparatus further comprises at least one cathode which can be a metalcathode. Mixtures of metals can be used.

The cathode can be used in conjunction with a solution comprising adissolved salt including a metal cation and an anion. In principle, anyion/metal combination where the ion can be reduced to the metal can beused for a cathode employing this method. More specifically, inprinciple, any elemental metal immersed in a solution containing ions ofthat metal, where the ions can be reduced to the elemental state inorder to facilitate the oxidation of the carbide ions to elementalcarbon, can be used. Examples include zinc metal in a solution of zincions, tin metal in a solution of stannous ions, silver metal in asolution of silver ions, and iron in a solution of ferrous ions. Inselecting the cathode, practical considerations can be taken intoaccount. For example, issues like corrosion of the metal cathode can beconsidered. Other factors to consider include, for example, thecharacteristics of the solvent and the overall solution and how theywould interact with the different components of the reaction system.Solubility of the various metallic salts in the different solvents orsolvent combinations would also be an issue.

In one embodiment, the electrochemical cell (e.g., galvanic cell)apparatus further comprises at least one metal cathode, wherein thecathode is a zinc, tin, iron (include steel), copper, or silver metalcathode. In another embodiment, the electrochemical cell (e.g., galvaniccell) apparatus further comprises at least one metal cathode, whereinthe cathode is a zinc or tin metal cathode.

In one embodiment, the galvanic cell apparatus anode is contacted withat least one first solution comprising at least one first solvent and atleast one first salt and a galvanic cell apparatus cathode is alsocontacted with at least one second solution comprising at least onesecond solvent and at least one second salt. The solvent and saltcombination for both the anode and cathode sides of the cell shouldprovide sufficient ionic conductivity for the process to be enabled. Theviscosity of the solvent can be also considered in solvent selection forfirst and second solvent. For first and second solvent, the solvent canbe, for example, a polar organic solvent such as an alcohol such asmethanol or ethanol, or an ether such as tetrahydrofuran, or an aproticsolvent such as DMSO or NMP. Examples of solvents include N-methylpyrrolidone, dimethyl formamide, acetone, tetrahydrofuran, pyridine,acetonitrile, methanol, ethanol, tetramethylurea, and/ordichlorobenzene. Mixtures of solvents can be used. In general, water isavoided in the solvent, and solvents can be dried. In some cases, slowreaction between the solvent and the carbide chemical compound mayoccur. For example, methanol can reaction with calcium carbide to formcalcium methoxide. Typically, the reaction apparatus should berelatively inert to the solvent so that side reactions are minimized oravoided.

The salts for the cathode and anode sides of the cell can be selected toprovide the cation or the anion which enable the reaction to work well.For example, the cathode metal being reduced can be used in conjunctionwith a salt which has the oxidized metal as cation. The anion of thesalt can be a halide such as fluoride, chloride, bromide, or iodide.However, the fluoride can cause a high heat of reaction which cangenerate problems so fluoride salts can be avoided. Chloride saltsgenerally are preferred. Examples of salts include zinc chloride,calcium chloride, stannous chloride, ferrous chloride, cupric chloride,silver chloride, aluminum chloride, lithium chloride, calcium fluoride,stannous fluoride, aluminum fluoride, and lithium fluoride.

An important factor also is that the cation of the carbide must form asoluble salt with the anion of the cathode cell. This may not bepossible in some cases such as some sulfate salts including calciumsulfate.

In one embodiment, the galvanic cell apparatus further comprises atleast one salt bridge and/or at least one ion exchange membrane. Ionexchange membranes are known in the art and typically are made of apolymeric material attached to charged ion groups. Anion exchangemembranes contain fixed cationic groups with mobile anions; they allowthe passage of anions and block cations. Cation exchange membranescontain fixed anionic groups with mobile cations; they allow the passageof cations and block anions. See, for example, Y. Tanaka, Ion ExchangeMembranes: Fundamentals and Applications, 2^(nd) Ed., 2015. Herein, theuse of ion exchange membranes can help prevent formation of unwantedside products and migration of undesired materials from one cell to theother cell.

In one embodiment, steps are taken so that the reaction is carried outunder anhydrous conditions. Moisture can be excluded to the extentneeded. Also, inert gases can be used such as argon or nitrogen.

The reaction time can be adapted to the need. Reaction time can be, forexample, one minute to 30 days, or one day to 20 days.

In one embodiment, the production of carbon is carried out without useof an external voltage source. The current flow from the spontaneousreaction is not controlled by external voltage in this embodiment.

In another embodiment, however, the galvanic cell apparatus comprises anexternal voltage source which is used to regulate the oxidationreaction, and in another embodiment, the production of carbon is carriedout with use of an external voltage source to regulate the oxidationreaction. This can also be called a “forced current” embodiment. Theapplication of an external voltage source allows one to control thevoltage over time using a controlled voltage over time curve, includinga step curve, for example. Constant voltage and/or constant currentregimes can be used. Over time, voltage can be increased or decreased.Reaction rate can be controlled and increased using the externalvoltage. For example, reaction rate (current flow in amperage) mightincrease at least ten times, or at least twenty times, or at least fiftytimes, or at least 100 time, or at least 250 times, for example, withthe application of external voltage compared to cases with no externalvoltage applied. The level of external voltage can be determined for aparticular system. One wants to avoid side reactions. One often willwant to increase reaction rate. Voltage can be, for example, 0 V to 40V, or 0 V to 30 V, or 0 V to 20 V, or 10 V to 20 V. The external voltagesource can be applied with use of a potentiostat as known in the art.

In one embodiment, the electrochemical cell apparatus is an electrolyticcell apparatus. Here, the reaction is not spontaneous, and an externalvoltage needs to be and is applied to drive the reaction. An example ismaking lithium or sodium.

The Carbide Chemical Compound Starting Material

Carbide chemical compounds or “carbides” are known in the art. See, forexample, Cotton & Wilkinson, Advanced Inorganic Chemistry, 4^(th) Ed.,1980, pages 361-363. This text classifies types of carbides as saltlikecarbides, interstitial carbides, and covalent carbides.

Known carbide chemical compounds include, for example, aluminum,arsenic, beryllium, boron, calcium, chromium (in five different Cr:Cratios), cobalt, hafniuim, iron (in seven different Fe:C ratios),lanthanum, manganese (in two different Mn:C ratios), magnesium (in twodifferent Mg:C ratios), molybdenum (in three different Mo:C ratios),nickel (in two different Ni:C ratios), niobium (in two different Nb:Cratios), plutonium (in two different Pu:C ratios), phosphorous,scandium, silicon, tantalum (in two different Ta:C ratios), thorium (intwo different Th:C ratios), titanium, tungsten (in two different W:Cratios), uranium (in two different U:C ratios), vanadium (in twodifferent V:C ratios), and zirconium carbide. Also, a carbide can formwith two different metals such as cobalt tungsten carbide.

In one embodiment, the carbide chemical compound is a salt-like carbideor an intermediate transition metal carbide. More particularly, thecarbide chemical compound is a salt-like carbide in one embodiment. Inanother embodiment, the carbide chemical compound is a methanide, anacetylide, or a sesquicarbide.

Methanides react with water to produce methane. Methane is a carbon atombonded to four hydrogen atoms in an sp3 hybridization. Two examples ofmethanides are aluminum carbide (Al₄C₃) and beryllium carbide (Be₂C).Acetylides are salts of the acetylide anion C₂ ⁻² and also have a triplebond between the two carbon atoms. Triple bonded carbon has an sp1hybridization and two examples of acetylides are sodium carbide (Na₂C₂)and calcium carbide (CaC₂). Sesquicarbides contain the polyatomic anionC₃ ⁻⁴ and contains carbon atoms with an sp1 hybridization. Two examplesof sesquicarbides are magnesium carbide (Mg₂C₃) and lithium carbide(Li₄C₃).

Sesquicarbides are of particular use for the preparation of sp1 carbon.One can produce Mg₂C₃ in the laboratory by bubbling methane throughmolten magnesium metal under an inert argon atmosphere at over 750° C.Other hydrocarbons such as pentane may also be viable candidates. Also,molten magnesium (Mg) reaction is another area of chemistry where littlehas been conducted. Research in molten Mg reactions have been limitedbecause of the dangers associated with molten Mg, especially with theprocess generating hydrogen gas as well. But a process very similar tothe synthesis of the magnesium sesquicarbide can be used to convertmethane directly into carbon in the form of graphite and hydrogen gas.Methane can be bubbled through a molten solution of Mg and magnesiumchloride salt. When heated to a temperature of over 750° C. under anargon atmosphere the elemental Mg metal and MgCl₂ both melt to form aliquid solution. Similar to the Mg sesquacarbide synthesis, methane isbubbled through the solution to produce either MgC₂ (magnesium carbide)or Mg₂C₃ and hydrogen gas that can be collected as a value addedproduct. The carbide then reacts with the metallic salt based on theoriginal chemistry of the carbon producing carbide reaction. The Mg₂C₃and MgCl₂ are converted to elemental carbon in the form of graphite,elemental Mg metal and MgCl₂, which would remain as part of the liquidsolution. Therefore, the Mg metal and MgCl₂ salt would remain unchangedthroughout the overall process while the methane would be converted topure carbon and hydrogen gas.

In particular embodiments, the carbide chemical compound is calciumcarbide, aluminum carbide, sodium carbide, magnesium carbide, lithiumcarbide, beryllium carbide, iron carbide, copper carbide, and chromiumcarbide. Sodium carbide has the advantage of being lighter.

In other more particular embodiments, the carbide chemical compound iscalcium carbide or aluminum carbide.

In another embodiment, the carbide chemical compound has sufficientelectronic conductivity to function as or in an anode. The conductivityfor different carbides can vary depending on factors such as purity andtemperature. However, one skilled in the art for a particularapplication can determine whether there is sufficient electronicconductivity and how to adapt the conductivity for the need. Forexample, the carbide chemical compound can have an electronicconductivity of at least 10⁻⁸ S/cm, or at least 10⁻⁷ S/cm, or at least10⁻⁶ S/cm, or at least 10⁻⁵ S/cm, or at least 10⁻⁴ S/cm, or at least10⁻³ S/cm, or at least 10⁻² S/cm, or at least 10⁻¹ S/cm, or at least 10⁰S/cm. The electronic conductivity of calcium carbide provides a usefulbenchmark for sufficient conductivity. No particular upper limit ispresent except for the limits provided by nature for a particularcarbide.

The form of the carbide chemical compound can also be varied. Forexample, it can be used in particle form or it can be used in the formof a monolithic material. In one embodiment, the carbide chemicalcompound is in the form of individual pieces or particles. In anotherembodiment, the carbide chemical compound is in the form of individualpieces or particles having a size of less than one cm. The mesh size ofparticles can be controlled.

The carbide chemical compound can be used in compositions and mixed withother ingredients such as binders or conductivity agents to the extentthe desired reaction can be achieved. In some embodiment, more than onecarbide chemical compound can be used.

One can use an electronically conductive binder to hold the pieces orparticles of carbide together. This can, for example, increase thesurface area of the carbide which is in direct contact with a conductivesurface. Electronically conductive binders also can be selected as a wayto produce composite materials where the conductive properties and othercharacteristics of the binder can be used to change the characteristicsof elemental carbon material produced. Examples of electronicallyconductive binders include conjugated polymers in doped or undoped formsuch a polythiophene or a polyaniline.

In one embodiment, the carbide is not silicon carbide.

Carbides are described further herein with respect to the apparatus andthe carbide electrode structure.

Temperature and Pressure

Relatively low temperatures, including room temperature, can be used forthe reaction to form carbon. For example, the temperature can be, forexample, about −50° C. to about 100° C., or about 10° C. to about 90°C., or about 0° C. to about 50° C., or about 15° C. to about 50° C. Thetemperature can be, for example, about 20° C. to about 30° C., or about23° C., 24° C., or 25° C. In some embodiments, one will want if possibleto avoid the expense of cooling, heating, and temperature controlelements. In some embodiments, one will want to run the reaction asclose to ambient as possible. As known in the art, in a largermanufacturing operation, excess heat from one point in the operation canbe transferred to another point in the operation which needs heat.

In some embodiments, the methods described herein are undertaken at roomtemperature.

The pressure can be about 1 atmosphere (760 torr) or normal pressure.The pressure can be, for example, about 720 torr to about 800 torr.Alternatively, the pressure can be for example about 0.5 atmosphere toabout 5 atmosphere, or about 0.9 atmosphere to about 1.1 atmosphere. Insome embodiments, one will want if possible to avoid the expense ofusing pressures below or above normal atmospheric ambient pressure. Onecan use a higher pressure to control the boiling point of the solvent.However, the equipment must be adapted to sustain high or low pressures.

A preferred embodiment is that temperature and pressure both are aboutambient so than expensive methods to control temperature and pressureare not needed. Hence, for example, the temperature can be about 20° C.to about 30° C., or about 25° C., and the pressure can be about 720 torrto about 800 torr, or about 760 torr.

Other Method Parameters

In one embodiment, one or more materials used in the process can berecycled. The material can be purified as part of the recycling. Forexample, solvent can be distilled and recaptured for further use. Saltscan be recaptured and reused.

In another embodiment, the current flow from a process reactor to makecarbon which is run as a galvanic cell can be used to help power anotherprocess reactor, including one used to make elemental carbon material,in which current is needed to help control the voltage.

The percent yield of the reaction for elemental carbon material productcan be controlled by the amount of current flow and the methods ofisolation as known in the art. Percent yield can be measured withrespect to the amount of carbon in the carbide chemical compound put inthe reactor. In some cases, the yield is at least one percent, or atleast 5%, or at least 10%, or at least 20%.

Organic Solvent Reaction to Produce Carbon from Carbide

A third aspect is provided for the production of elemental carbonmaterial at normal temperature and pressure but without anelectrochemical apparatus. Here, a method is provided comprising:producing elemental carbon material from the oxidation of carbide in atleast one carbide chemical compound (e.g., calcium carbide) which is incontact with a solution comprising at least one organic solvent (e.g.,methanol) and at least one dissolved salt (e.g., calcium chloride)comprising at least one metal cation which is reduced. The cation isselected so that a spontaneous reaction can occur wherein the carbide isoxidized and the metal cation is reduced. However, in this embodiment,the molten salt approach of U.S. application Ser. No. 14/213,533 and PCTApplication PCT/US2014/028755 and the electrochemical approach describedherein are not used. Rather, in this embodiment, the reaction can becarried out in a single reaction container and need not be split intotwo cells as is done with the electrochemical reaction.

In this embodiment, the temperature and pressure can be as describedabove. Normal temperature and pressure can be used.

The carbide chemical compound can be as described herein using, forexample, aluminum carbide or calcium carbide. The selection of salts,cations, and anions also can be made as described herein.

Examples of the organic solvent include solvents listed herein for theelectrochemical reaction such as an alcohol such as methanol or ethanolas described herein. Polar solvents are needed which can dissolve asalt. Aprotic solvents can be used. Ideally, the solvent would not reactwith carbide. Alternatively, it reacts with carbide but only veryslowly.

The elemental carbon material produced is described herein also.

The reaction time can be adapted to the need.

Anhydrous reaction conditions can be used. For example, a dry box can beused to avoid side reactions with water or oxygen.

III. Apparatus

Another aspect provides for an apparatus which can be used to carry outthe methods described herein, including an apparatus comprising at leastone electrochemical cell comprising: at least one anode comprising atleast one carbide chemical compound, and at least one cathode. Thisapparatus can be used to carry out the methods described and/or claimedherein including those described in Part II of this application. Again,carbide electrode structures which can be used in the apparatus aredescribed further in, for example, Part IV of this application. Again,elemental carbon material reaction products are described further inPart V of this application. Other embodiments include methods of makingthese apparatuses. A plurality of apparatuses can be used in a largersystem if desired.

The electrochemical apparatus can be a galvanic cell apparatus or anelectrolytic cell apparatus. The galvanic cell is preferred.

In one embodiment, the carbide chemical compound is a salt-like carbideor an intermediate transition metal carbide. In one embodiment, thecarbide chemical compound is a salt-like carbide. In one embodiment, thecarbide chemical compound is a methanide, an acetylide, or asesquicarbide. In one embodiment, the carbide chemical compound iscalcium carbide, aluminum carbide, sodium carbide, magnesium carbide,lithium carbide, beryllium carbide, iron carbide, copper carbide, andchromium carbide. In one embodiment, the carbide chemical compound iscalcium carbide or aluminum carbide. In one embodiment, the carbidechemical compound has sufficient electronic conductivity to function asan anode. In one embodiment, the carbide chemical compound has anelectronic conductivity of at least 10⁻⁸ S/cm, or at least 10⁻⁷ S/cm, orat least 10⁻⁶ S/cm, or at least 10⁻⁵ S/cm, or at least 10⁻⁴ S/cm, or atleast 10⁻³ S/cm, or at least 10⁻² S/cm, or at least 10⁻¹ S/cm, or atleast 10⁰ S/cm. The electronic conductivity of calcium carbide providesa useful benchmark for sufficient conductivity. No particular upperlimit is present except for the limits provided by nature for aparticular carbide.

In one embodiment, the carbide chemical compound is in the form ofindividual pieces or particles. In one embodiment, the carbide chemicalcompound is in the form of individual pieces or particles having a sizeof less than one cm.

In another embodiment, the carbide chemical compound is in the form ofan integral material or an ingot of material.

In one embodiment, the carbide chemical compound is held in a container.

In one embodiment, the galvanic cell apparatus anode is contacted with asolution comprising at least one solvent and at least one salt.

In one embodiment, the electrochemical cell apparatus anode is contactedwith a solution comprising at least one organic solvent and at least onedissolved salt, as described above. In one embodiment, theelectrochemical cell apparatus cathode is contacted with a solutioncomprising at least one organic solvent and at least one dissolved saltas described above. In one embodiment, the electrochemical cellapparatus cathode is a metal cathode as described above. In oneembodiment, the electrochemical cell apparatus cathode is a metalcathode, wherein the metal is zinc, tin, iron, copper, or silver. In oneembodiment, the electrochemical cell apparatus cathode is a metalcathode, wherein the metal is zinc or tin.

In one embodiment, the electrochemical cell apparatus comprises anexternal voltage source to regulate an oxidation reaction of carbide inthe carbide chemical compound. For example, a potentiostat can be usedto provide such an external voltage which can be varied.

Apparatus schematics are provided in FIGS. 2-5 and 19. FIGS. 17 and 18show actual smaller scale apparatuses for carrying out the reactions.FIGS. 20-23 show a larger apparatus and elements of the apparatus.

There are several improvements to the reactor in FIG. 18 from thereactor of FIG. 17. The first is cells are slightly larger allowing forgreater volume of solvent and to accommodate to volume occupied by thereference electrodes that can be added to the various experiments. Theaddition of the ports on the sides of the cell is also to accommodatethe addition of various electrodes and monitoring devices. The otherimprovements include the increased diameter of the salt which tofacilitate the greater transfer of ions. Finally, the reactor wasdesigned and fabricated in two separate pieces held together by aglassware clamp. This allows an ion exchange membrane to be installed inthe salt bridge.

In one embodiment, the apparatus is adapted for carrying out the methodsdescribed and/or claimed herein.

IV. The Carbide Electrode Structure and Methods of Use

The carbide chemical compound can be used in and adapted for use in anelectrode structure. Hence, yet another aspect provides for an electrodestructure comprising at least one carbide chemical compound, whereinoptionally the carbide chemical compound is a salt-like carbide; and atleast one electronically conductive element different from the carbidechemical compound. This electrode structure can be used to carry out themethods and to prepare the apparatuses described and/or claimed herein.Embodiments described herein also include methods of making and methodsof using the carbide electrode structure. Multiple electrode structurescan be used as part of a larger electrode system. The shape of theelectrode can be varied for the need. The conductivity of the electrodecan be adapted to the need. The solid properties and macro-, micro-, andnano-scale morphology, such as the size and shapes of openings,porosity, and pore size, can be adapted to the need.

The solid electrode structure and the carbide chemical compound can becontacted with at least one liquid for a redox reaction. The electrodestructure provides a reaction of the carbide chemical compound which isnot just a surface reaction but can extend to the internal structure ofthe carbide chemical compound. While the present inventions are notlimited by theory, it is believed that the carbon carbide layer of thecarbon compound at the surface is reacted to form elemental carbonmaterial as the cation (e.g., calcium) is transported away from thecarbon into solution. Multiple layers of carbon can be built up. Thesurface of the carbide can have some porosity.

The carbide electrode can be an electrode (an anode) where the chemicalreaction can occur within the electrode instead of just at the surface.The electrode material itself (e.g., calcium carbide) is being consumedin the reaction where the calcium ion dissolves into the solution andthe elemental carbon material is remaining.

In one embodiment, the carbide chemical compound is a salt-like carbideor an intermediate transition metal carbide. In one embodiment, thecarbide chemical compound is a salt-like carbide. In one embodiment, thecarbide chemical compound is a methanide, an acetylide, or asesquicarbide.

In one embodiment, the carbide chemical compound is calcium carbide,aluminum carbide, sodium carbide, magnesium carbide, lithium carbide,beryllium carbide, iron carbide, copper carbide, and chromium carbide.In one embodiment, the carbide chemical compound is calcium carbide,aluminum carbide, sodium carbide, magnesium carbide, lithium carbide, orberyllium carbide. In one embodiment, the carbide chemical compound iscalcium carbide or aluminum carbide. In one embodiment, the carbidechemical compound has sufficient electronic conductivity to function asan anode. In one embodiment, the carbide chemical compound has anelectronic conductivity of at least 10-8 S/cm or other ranges describedherein such as at least 10-7 S/cm, or at least 10-6 S/cm, or at least10-5 S/cm, or at least 10-4 S/cm, or at least 10-3 S/cm, or at least10-2 S/cm, or at least 10-1 S/cm, or at least 100 S/cm. No particularupper limit is present except for the limits provided by nature for aparticular carbide. In one embodiment, the carbide chemical compound isan ionically bonded solid.

In one embodiment, the carbide chemical compound is in the form ofindividual pieces or particles. In one embodiment, the carbide chemicalcompound is in the form of individual pieces or particles having a sizeof less than one cm. In one embodiment, the carbide chemical compound isproduced in a form to provide maximum or large amounts of surface area.This can facilitate reaction of the carbide at its surface. The particlesize and surface area can be adapted to the multiple needs.

In one embodiment, the carbide chemical compound is a single monolithicpiece or a series of monolithic pieces. For example, calcium carbide istypically formed in large ingots. The ingots are then crushed andclassified to the proper piece or particle size before going out asfinal product. One can maintain the large ingots to preserve the largecrystals of calcium carbide produced. This would in turn allow for largesingle sheets of graphene to be produced using the electrochemicalmethods described herein.

In one embodiment, one can take the large ingot of calcium carbideproduced as one solid piece. One hole (or even several holes) can bedrilled or bored out where it can then be connected to a currentcollector. The current collector can be, for example, any metal with amelting point lower than the melting point of the calcium carbide.Alternatively, metals with melting points higher than that of calciumcarbide can be used. However, these would probably be specialized alloysto withstand those temperatures.

This metal would also be electrically conductive and preferably inert inthe solvent/salt combination used for the reaction. A rod of the metalcan be inserted into the whole board out in the calcium carbide ingot.The rod would then be “welded” to the single piece of calcium carbide bypouring a molten form of the metal into the gap between the rod in thehole bored out in the calcium carbide. The molten metal would acteffectively as a weld connecting the two. This is similar to howelectrodes are made for the aluminum industry.

A second method can be done by fabricating a structure like a cage orsomething similar to tresses used in buildings. Any type of shape orstructure that includes empty space and provides a high surface area canbe used. The structure would be made out of a conductive material thatis stable at the temperatures of carbide production or around 2000° C.Another desired characteristic would be that the material would be inertto the solvent/salt solution used in the electrolysis reaction. Graphitecan be an ideal material for this application. Another possibility couldbe some type of metal alloy that is stable to high temperatures. Thestructure could then be placed into the ingot where the solid piece ofcalcium carbide is formed. The calcium carbide would form around thecurrent collector. Then the calcium carbide formed and the currentcollector can be removed as one single piece and used as the carbideelectrode.

In some embodiments, the carbide chemical compound can be used with oneor more additional, different materials such as an additive. Materialsand additives which are useful for making electrodes can be used. Forexample, a binder can be used.

In one embodiment, the carbide chemical compound is held in a container.In one embodiment, the container has openings which allow fluid, such asan electrolyte, to enter the container and contact the carbide chemicalcompound

In one embodiment, the carbide chemical compound is divided intoportions. In one embodiment, the carbide chemical compound is dividedinto approximately equal portions.

In one embodiment, the carbide chemical compound is at least about 80wt. % pure, or at least 90 wt. % pure, or at least 95 wt. % pure, or atleast 97 wt. % pure.

The electronically conductive element should have good electronicconductivity such as, for example, at least 10⁻³ S/cm, or at least 10⁻²S/cm, or at least 10⁻¹ S/cm, or at least 10⁰ S/cm.

In one embodiment, the electronically conductive element is a binder forthe carbide chemical compound.

In one embodiment, the electronically conductive element is adapted tobe non-reactive with the reaction media. For example, it should be inertto the contacting solution, or at least inert enough to effectivelyconduct the reaction for the need.

In one embodiment, the electronically conductive element is a containerand the carbide chemical compound is held in the container.

In one embodiment, the electronically conductive element is a metalliccontainer and the carbide chemical compound is held in the metalliccontainer. In one embodiment, the electronically conductive element is anon-metallic container such as graphite and the carbide chemicalcompound is held in the non-metallic container such as graphite. Forexample, graphite baskets can be used.

In one embodiment, the electronically conductive element comprises atleast one conductive rod.

In one embodiment, the electrode structure is adapted to be removablyattached to an apparatus.

In one embodiment, the electronically conductive element of theelectrode structure comprises at least one current collector.

In one embodiment, the electrode structure is adapted for use as ananode in, for example, an electrochemical cell apparatus.

For example, provided is a method comprising operating at least oneanode in an electrochemical cell, wherein the anode comprises at leastcarbide chemical compound which includes a method comprising operatingat least one anode in a galvanic cell, wherein the anode comprises atleast carbide chemical compound. The electrochemical cell apparatus canbe a galvanic cell apparatus or an electrolytic cell apparatus. Theapparatus can be used for production of elemental carbon material.However, other embodiments are possible for uses other than theproduction of elemental carbon material. Other uses of the apparatuswith the carbide electrode include oxidation reactions such as, forexample, conversion of aldehyde to carboxylic acid, and oxidation of ametal such as ferrous ion to ferric ion. Such reactions could be usefulin, for example, environmental processes such as, for example, acid minedrainage or sewage treatment.

In most cases, the one or more carbide chemical compounds is the onlyelectrochemically reactive moiety participating in the oxidation part ofthe redox reaction. In one embodiment, the anode electrochemicallyactive material consists essentially of at least one carbide chemicalcompound. In another embodiment, the anode electrochemically activematerials consist of at least one carbide chemical compound. Here, aconductor such as a metal which is not oxidized or reduced in the anodeis not considered an electrochemically active material.

V. The Elemental Carbon Material as Reaction Product

Still further, another aspect provides for an elemental carbon materialcomposition prepared by the methods, or with use of the apparatuses orcarbide electrode structures, described and/or claimed herein. Theelemental carbon material can be described and/or claimed by thecharacteristics of the elemental carbon material and/or by how it wasmade. Elemental carbon materials are materials known in the art to focuson the carbon content and do not include organic compounds such asmethane, methanol, or acetic acid. Examples such as graphite and diamondare well-known as elemental carbon materials. These compositions canrange from the compositions as initially prepared from the carbidechemical compound to the compositions as they exist after one or moretreatment, purification, and/or separation steps (post-processing stepsincluding exfoliation and doping steps, for example). The compositionscan be mixtures of different forms of the elemental carbon material. Thecomposition can comprise crystalline portions and/or amorphous portions.The carbon can be in the form of one or more graphene layers, and it canbe in an exfoliated form. Preferred embodiments for graphene includeatomically thin single sheet graphene or few layer graphene. Graphenecan have 1-10 layers for example. Thicker forms of graphene also can beof interest. Also, the elemental graphene material, including grapheneforms, can be disposed on substrate films.

Characterization methods for elemental carbon materials are well knownand include analysis of microstructure, morphology, and physicalproperties. For example, carbon black materials are well known andcharacterized as described in, for example, (1) Carbon Black:Production, Properties, and Uses (Sanders et al., Eds.), and (2) CarbonBlack: Science and Technology, 2^(nd) Ed., (Donnet et al., Eds.) 1993.Morphological properties of elemental carbon materials include, forexample, particle size, surface area, porosity, aggregate size, andaggregate shape. Physical properties include density, electronic,thermal, bulk, and impurities. Microstructure analysis includes XRD,Dark Field Electron Microscopy, Oxidation Studies, Diffracted BeamElectron Microscopy, Phase Contrast TEM imaging, and High ResolutionSEM, STEM, STM, SFM, and AFM imaging.

Other characterization methods for carbon are known and describedfurther herein. See, for example, review article by Chu et al.,Materials Chemistry and Physics, 96 (2006), 253-277, which describescharacterization of amorphous and nanocrystalline carbon films. Methodsdescribed include optical (Raman, both visible and UV, and IR), electronspectroscopy and microscopy (e.g., XPS, AES, TEM of various kinds, andEELS), surface morphology (AFM, SEM), NMR, and X-ray relectivity.Methods described include how to measure sp2:sp3 ratios.

The elemental carbon material can provide many novel, interesting, anduseful structures when viewed under an SEM, including at a 200 micronscale bar view or less as shown in the Figures. Features shown in theSEM figures can be used to describe and claim the elemental carbonmaterials. Spots on the elemental carbon material also can be selectedfor Raman spectroscopy, and Raman data can also be used to describe andclaim the elemental carbon materials. Other data such as EDAX and XRDcan also be used to describe and claim the elemental carbon materials.

Generally, high purity elemental carbon materials are desired. In oneembodiment, the elemental carbon material is more than 70%, or more than80%, or more than 90%, or more than 95%, or more than 98%, or more than99% (atomic percentage) carbon. This percentage can be measured by, forexample, elemental analysis methods including SEM-EDAX. Of course, insome embodiments, less high purity may be acceptable. Also, in someembodiments, non-carbon elements can be deliberately incorporated suchas in a doping process.

In one embodiment, the elemental carbon material is more than 50%, ormore than 60%, or more than 70%, or more than 80%, or more than 90% sp2carbon. A combination of analytical techniques can be used to determinean accurate estimate. For example, there is also the possibility ofanalysis using bromine. Sp2 carbon absorbs a certain amount of brominerelative to amorphous carbon or even possibly sp1 carbon if we canproduce it. Sp3 carbon does not absorb bromine at all. Therefore, we maybe able to quantitatively determine these percentages using a type ofbromine absorption test.

In one embodiment, the elemental carbon material is more than 50%, ormore than 60%, or more than 70%, or more than 80%, or more than 90% sp3carbon.

In one embodiment, the elemental carbon material comprisestwo-dimensional plate-like structures. These structures can be stackedon top of one another. In another embodiment, the elemental carbonmaterial comprises three-dimensional structures.

In some embodiments, the elemental carbon material has amorphous carboncontent. In other cases, crystalline carbon can be present.

In some cases, particles can be isolated, and average particle size(d₅₀) can be, for example, 500 nm to 500 microns, or one micron to 100microns, or two microns to 50 microns, or 10 microns to 30 microns. Ifdesired, nanoscopic particles can be isolated with average particle sizeof less than 500 nm such as, for example, 10 nm to 500 nm, or 20 nm to100 nm. Commercial particle size analyzers can be used to measureparticle size.

The elemental carbon material, at various stages of purification andisolation, can be tested by methods known in the art including, forexample, optical microscopy, electron microscopy including scanningelectron microscopy (SEM) and transmission electron microscopy (TEM),energy dispersive x-ray analysis (EDX), Raman and FTIR spectroscopy,x-ray diffraction, X-ray photoelectron spectroscopy (XPS), Augerelectron spectroscopy (AES), low energy and high energy electron energyloss spectroscopy (EELS), neutron scattering, ellipsometry, electricalresistance, and atomic force microscopy (AFM). Particle analysis canalso be carried out including measurement of particle size and surfacearea. Electrochemical testing can also be carried out. Tribology, wear,friction, indentation, modulus, hardness testing can also be carriedout.

For Raman spectroscopy, a G band (around 1590 cm⁻¹) can be present incrystalline graphite and a D band (around 1345 cm⁻¹) can be presentassociated with disordered graphite. The ratio of the two bands can beused to characterize the degree of graphitization and the graphitecrystallite size.

The elemental carbon material produced can be analyzed by surfaceanalytical methods such as AFM or XPS. For example, XPS analysis canshow higher levels of oxygen at the surface than in the bulk material.This can mean that the surface of the material had formed grapheneoxide. Graphene oxide, in principle, could be formed as part of thereaction or due to the separation and purification operations. Othersurface elements can include O, H, N, S, and halogens.

In another embodiment, the elemental carbon material comprises sp1carbon material. In some embodiments, the methods described herein canbe used to produce an allotrope of carbon that is C₇₀. In someembodiments, the methods can be used to produce an allotrope of carbonthat is C₆₀. Other kinds of fullerenes can be made. In some embodiments,the methods described herein can be used to produce an allotrope ofcarbon that is Herringbone Multi Wall Carbon Nano Tubes (“MWCNT”).Single-walled carbon nanotubes also can be made. In some embodiments,the methods described herein can be used to produce an allotrope ofcarbon that is Cylindrical MWCNT. In some embodiments, the methodsdescribed herein can be used to produce an allotrope of carbon thatcomprises carbon fibers.

The methods described herein can produce carbon with sp¹, sp², and/orsp³ hybridization, as well as mixtures thereof. The sp¹ hybridizedcarbon can be in the form of carbyne. The sp² hybridized carbon can bein the form of carbene, graphite, and/or graphene. The sp³ hybridizedcarbon can be in the form of diamond.

Particular carbon materials may thus be produced through the applicationof external voltage to an electrolysis cell wherein at least one of theelectrodes is a carbide.

In some embodiments, the methods described herein can be used to producean allotrope of carbon that is sp² hybridized, and contains no sp³hybridization. In some embodiments, the methods described herein producean allotrope of carbon that is sp³ hybridized, and contains no sp²hybridization. In some embodiments, the methods described herein producean allotrope of carbon that is sp¹ hybridized and contains neither sp²or sp³ hybridization.

In some cases, the elemental carbon material can have more sp2 than sp3hybridized carbons, and in other cases, the elemental carbon materialcan have more sp3 than sp2 hybridized carbons. The ratio of sp2:sp3 canbe, for example, 1:10 to 10:1, or 1:8 to 8:1, or 1:6 to 6:1, or 1:4 to4:1, or 1:2 to 2:1.

The methods described herein can be used to produce a product that ismore than 50%, more than 55%, more than 60%, more than 65%, more than70%, more than 75%, more than 80%, more than 85%, more than 90%, morethan 95% sp¹ hybridized.

In an embodiment, the methods described herein produce a product that ismore than 50%, more than 55%, more than 60%, more than 65%, more than70%, more than 75%, more than 80%, more than 85%, more than 90%, morethan 95% sp² hybridized.

In some embodiments, the methods described herein produce a product thatis more than 50%, more than 55%, more than 60%, more than 65%, more than70%, more than 75%, more than 80%, more than 85%, more than 90%, morethan 95% sp³ hybridized.

In some embodiments, the methods described herein produce a product thatis more than 50%, more than 55%, more than 60%, more than 65%, more than70%, more than 75%, more than 80%, more than 85%, more than 90%, morethan 95% sp² hybridized in the form of graphite.

In some embodiments, the methods described herein produce a product thatis more than 50%, more than 55%, more than 60%, more than 65%, more than70%, more than 75%, more than 80%, more than 85%, more than 90%, morethan 95% sp hybridized in the form of diamond.

Large area pieces of carbon, having high levels of elemental carbonpurity, are of particular interest. They can be, for example, a sourcefor large area graphene. The piece may have a lateral dimension of, forexample, at least one mm, or at least two mm, or at least one cm, or atleast two cm. The lateral dimension can be a length or a width of apiece or particle. In some cases, both the length and the width can beat least 1 mm, or at least 2 mm, or at least 1 cm, or at least two cm.The volume of the piece can be, for example, at least one cubic mm, orat least one cubic cm (cc), or at least 8 cubic cm (cc). Also importantare forms of carbon having flat surfaces whether of lower or higher flatsurface area.

Carbon structures are shown in the SEM and optical photographs providedherein which can be of commercial use. In many cases, it is desired tohave crystalline forms of the elemental carbon material rather thanamorphous forms.

In some embodiments, the elemental carbon material comprises at leastsome two-dimensional plate-like structures. In some embodiments, theelemental carbon material comprises at least some two-dimensionalplate-like structures stacked on top of one another. Graphene structuresmay be evident. Thicker graphene structures can be converted to thinnergraphene structures. In some embodiments, the elemental carbon materialcomprises at least some three-dimensional structures.

In some embodiments, the elemental carbon material shows porousstructures or voids.

In some embodiments, bent structures can be seen. The bent structure canbe characterized by an acute angle, and the angle can be controlled bythe synthesis method. In other embodiments, rods can be formed. In someembodiments, curved elemental particles can be observed. In someembodiments, perpendicular features can be observed.

Further structures can be observed with higher resolution analyticalmethods.

VI. Post Reaction Processing of Elemental Carbon Material

After forming in the apparatus, the elemental carbon material can befurther treated beginning with, for example, purification and/ormechanically changing the form into powder or particle forms. Treatmentscan be mechanical or chemical. The piece of product can be subjected tovarious mechanical steps such as grinding, exfoliation, or polishingsteps. Additional treatment steps can include, for example, doping andintercalation steps. Some of the elemental carbon material may beattached to the electrode and will need to be removed from theelectrode. Other elemental carbon material may leave the electrodeduring the reaction and may, for example, sink to the bottom of thereaction cell for collection.

PCT Application PCT/US2014/028755, filed Mar. 14, 2014 and published asWO 2014/144374, also describes a method of making carbon from carbideand metal salts in a thermal process, and also describes various postreaction processing steps which can be used.

In another embodiment, the elemental carbon material is removed andtreated with acid and washed or flushed with water. Strong acids such asHCl can be used.

In one embodiment, the elemental carbon material can be converted toparticle form, and the particles separated based on particle size.

Graphene exfoliation steps are known in the art and described in, forexample, Bonaccorso et al., Materials Today, December 2012, 15, 12, 564.In particular, large area graphene sheet production is of interest. Thelarge pieces of elemental carbon material produced by methods describedherein can enable production of large area graphene. A solvent such asNMP can be used for exfoliation. Sonication can also be used forexfoliation. Larger pieces of carbon in many cases require higher powerto exfoliate. The exfoliation process can be controlled so as to controlthe thickness of the exfoliated product, such as graphene.

Also described herein are derivative compositions associated with theelemental carbon material compositions described herein. For example,the elemental carbon material compositions described herein can be mixedwith or doped with other elements, compounds, ingredients, additives,and/or materials.

VII. Applications

Selected representative examples of applications are described below.Devices, apparatuses, systems, kits, methods of making, and methods ofusing that are associated with these applications are also describedherein including devices, apparatuses, systems, and kits which comprisethe elemental carbon materials and their derivatives described herein(e.g., battery, fuel cell, or filtration devices). The elemental carbonreaction products, whether in bulk form, microscale form, or nanoscaleform, can be used in a wide-variety of applications including, forexample, applications generally known for carbon materials includingapplications known, more specifically, for graphite materials,applications known for diamond materials, applications known foramorphous carbon, and applications known for nanoscale forms of carbon,for example. In some cases, the elemental carbon material can be mixedwith one or more other ingredients for application use.

Carbon black, for example, is used as filler, pigment, toners, andreinforcement agent.

Many applications relate to the electrically conductive properties ofcarbon and the electronics and semiconductor industries. For example,carbon inks are known including conductive inks Carbon-based fillers orconductive agents are known.

Activated carbon has many applications.

Graphite is a material found in nature and also is syntheticallyproduced. Examples of natural graphite are flake, crystalline, andamorphous graphite. Graphite flakes can have flat, plate-like particleswith hexagonal or angular edges. The percent carbon can impact theapplication. Graphite can be used as electrodes, pastes, brushes,crucibles, lubricants, foundry facings, moderator bricks in atomicreactors, paints, pencils, brake linings, foundry operations, refractoryapplications, steel making, lithium-ion batteries, fuel cells, and thelike.

In particular, batteries including lithium and lithium-ion batteries canbe an application, as well as air batteries such as zinc air batteries.Lithium-ion batteries are described in, for example, Yoshio et al.(Eds.), Lithium-Ion Batteries: Science and Technologies, includingchapter 3 (pages 49-73) and chapter 18 (pages 329-341) which focus oncarbon anode materials, as well as chapter 5 (pages 117-154) whichfocuses on carbon-conductive additives and chapter 22 (pages 427-433)which focuses on novel hard-carbon materials.

Graphene can be used in advanced semiconductor devices. Large areagraphene is important. Other applications include filters (includingwater filtration and desalinization of sea water), batteries, touchscreens, capacitors, fuel cells, sensors, high frequency circuits,flexible electronics, computing, data storage, solar, and photovoltaics.

Diamonds can be low quality or high quality and are applied inapplications which use hardness including abrasion resistant materials,as well as drilling, polishing, and cutting materials. Diamonds also canbe used for sensors, electronics, medical imaging, semiconductors, supercomputers, and sonar. Diamonds also can be gems.

Carbon related materials such as CaC₆ have been shown to besuperconducting. Other applications for sp1 materials relate to use ofsuperconductor materials and even high temperature or room temperaturesuperconductor materials.

Carbon nanotube products can be in the form of “forests” of microscopictubular structures. They can be used in, for example, baseball bats,aerospace wiring, combat body armor, computer logic components, andmicrosensors in biomedical applications. Carbon nanotubes also can beused in lithium ion batteries and various sporting equipment.

Preferred Embodiments and Working Examples

In an illustrative embodiment, an electrode in an electrochemical cellcomprises or is comprised of calcium carbide and is immersed in asolution of methanol and calcium chloride salt. As the carbide electrodeis an ionic solid which is electrically conductive, the carbideelectrode allows for the oxidation of the acetylide anion to occur inthe solid state. As a counter cell, a polished piece of zinc is immersedin a solution of zinc chloride in methanol. Alternatively, because thereduction potential of tin is higher than the reduction potential ofzinc, in an aspect, elemental tin in a stannous chloride solution can beutilized instead of zinc in zinc chloride. When an electrical connectionis established between the cells through a salt bridge, the oxidation ofcarbide anion reaction and the reduction of zinc cation reaction canoccur at room temperature. Thus, the voltage of the reaction can bedirectly read.

The galvanic reaction apparatus of preferred embodiments differs from aconventional galvanic apparatus in several respects. First, the zincelectrode is the cathode in the process while the carbide electrode isthe anode. At the cathode, the Zn²⁺ ions from the ZnCl₂ in solution arereduced (gain electrons) to elemental zinc which plates out on thesurface of the zinc electrode. The Cl⁻ ions from the ZnCl₂ in solutionare the counter ions that migrate across the salt bridge to balance thecharge from the flow of electrons. At the anode in the carbide cell, theC₂ ²⁻ from the solid calcium carbide is oxidized (loses electrons) toform elemental carbon and the Ca²⁺ ions enter the solution inside thecarbide cell.

In exemplary embodiment of the electrolysis apparatus of the invention,calcium carbide loaded into stainless steel baskets forms the anode inthe carbide cell. The stainless steel rod and baskets which hold thecalcium carbide are essentially an extension of the wire connecting thecathode and the anode.

The resulting apparatus is unique in that the calcium carbide is anionic solid which is electrically conductive. Therefore, the oxidationreaction is believed to occur in the solid phase where the carbide anion(C₂ ²⁻) is oxidized to elemental carbon. This is substantially differentfrom a reaction in which the anions are oxidized in the liquid phasefrom the solution. In addition, the Ca²⁺ ions entering the solution areunchanged (not oxidized) from their state in the solid phase.

For verification, in a preferred embodiment, the voltage of a standardsilver/silver chloride cell to the zinc/zinc chloride cell is comparedusing a salt bridge. In an embodiment, the salt bridge is a saturatedcalcium chloride solution in methanol. This permits migration of thechloride to the silver/silver chloride cell and calcium ions to thezinc/zinc chloride cell needed to maintain electro neutrality. Thevoltage of the silver/silver chloride cell is subtracted from the cellvoltage to yield the zinc/zinc chloride potential. Once the potential isknown, the potential of the calcium carbide cell can be determined.Since the products of the carbide cell are not mixed with anynon-water-soluble material, they can be cleaned and the productsanalyzed.

This can help to provide a method to determine the voltage necessary toproduce a specific product.

In an embodiment, an electrochemical cell enables the production of theentire range of carbon materials in their various states.

In an embodiment, an electrochemical cell as described herein includes(1) an electrode, for example a solid electrode, (2) a conductor, forexample a conductor in a lower or elemental valence state; and (3) anelectrode, for example an electrode immersed in a solution that containsions of the electrode material. The solution is conductive. That is, theions can be mobile and can migrate under the influence of an electricalpotential.

The Latimer series is a compilation of the electrochemical potentialsbetween the metal and a standard solution of its ions in the conductingsolution. Two such cells with different electrochemical potentials canbe used to make either an electrolytic or a galvanic apparatus; one cellis oxidizing, losing electrons and the other cell is reducing, gainingelectrons. If the cell is reducing, then electrons from the oppositecell, the oxidizing cell, accumulate on the electrode surface. Positiveions from the solution migrate to the electrode and electrons are pickedup by the ions that are subsequently reduced sometime to the elementalstate where they plate out on the electrode surface. If the cell isoxidizing, electrons leave the electrode and go to the reducingelectrode. The material on the oxidizing electrode dissolves into thesolution as positive ions.

In the carbide cell, the carbon anion in the calcium carbide can give upelectrons and become elemental carbon. The calcium cation can dissolvein the solvent and requires anions to be dissolved in the solvent. Theelectrons from the carbide anion will pass through the circuit to themetal electrode in the reduction cell. This will attract cations of themetal from the solution and as they receive the electrons from the anionoxidation they will be reduced and plated out on the metallic electrode.This provides an abundance of anions that fulfill the deficit needed bythe calcium ion in the other cell. A salt bridge is used to balance thecations and anions in the apparatus. The salt bridge is a connection ofa salt solution to both cells. The anions from the salt bridge travel tothe oxidizing electrode while the cations from the salt bridge travel tothe reducing electrode. The difference in electrode potentials drivesthe cell.

A galvanic cell, such as that represented in FIG. 2, depends on thevoltage potential from the chemical reaction to cause electron flow. Acell, like that shown in FIG. 3, may use an external power source, suchas a battery or potentiostat, to drive or regulate the chemicalreactions. The exact potential can be controlled by an external variableresister but is limited by the range of reactions than can occur in thecells. The application of the different potentials can determine theproducts produced by controlling the chemistry that can occur in thecells as chemical reactions are limited by the potential.

Under such a system, the voltage can be adjusted through the variableresister to any desired voltage within the available potential. Thecurrent can be permitted to flow until an appropriate quantity ofproduct is produced in the carbide cell for isolation and analysis. Thevoltage can be altered until another current flows and the procedure canbe repeated until all the various materials have been isolated andtested. In an embodiment, the zinc cell voltage is measured against thestandard silver/silver chloride cell, and also monitored.

The calcium chloride or other associated salt is soluble in the solventand the solution is conductive to produce the oxidative cell. Theoxidative cell may then be attached to a second cell, the reducing cell,though a salt bridge. The salt bridge may be made from the same solventand saturated with the same calcium salt or another suitable salt. Inanother embodiment, the reducing cell contains an elemental metal as anelectrode immersed in a salt solution of that metal as a cation in thesame solvent.

As demonstrated by the Examples described below, the specific allotropesproduced using the apparatus of the invention vary depending on thevoltage potential between the cells of the apparatus. In theelectrolytic cells according to some embodiments of the invention, oneelectrode is connected to a voltmeter and one end of a power supply andthe other electrode is attached to a variable resister. The second armof the power supply is attached to the variable resister so the resistercan control the voltage between the two-electrode cell circuits. Thus,the circuit can permit any voltage, and therefore any potential. Thisallows the production of particular desired allotropes and themaintenance of a particular voltage level to enhanec the purity of aparticular allotrope.

In some embodiments, the methods described herein can be undertakenusing a galvanic cell reactor. The reactor can be comprised of multipleparts, including a carbide cell and a zinc cell. In some embodiments,the reactor comprises a carbide electrode. In some embodiments, thecarbide cell and the zinc cell are connected by a salt bridge. Thecarbide cell can comprise electrode baskets, which can contain thesalt-like carbide. The electrode baskets can comprise fine mesh (20-60mesh) stainless steel screens. The salt-like carbide in the electrodebaskets can then be immersed in a solution comprising a chloride salt.The carbide cell can be connected to a circulation pump, which can drawthe solution from below the level of the electrode and salt bridge andpumps it back into the top of the carbide cell, creating a flow of thesolution vertically in the cell. An inert gas (e.g. argon) can be inputnear the bottom of the carbide cell, bubbled through the solution, andremoved from the carbide cell through the vapor trap. The inert gas flowcan maintain an inert environment inside of the cell and generatesadditional agitation between the carbide and the solution.

In some embodiments, the zinc cell comprises a zinc electrode immersedin a solution of zinc chloride dissolved in the solvent (driedmethanol). The zinc electrode can include a rod of elemental zinc.Attached to the zinc rod may be a basket filled with mossy zinc (i.e.,irregular pieces of elemental zinc) wherein the rod can pass through themiddle of the basket and allow the mossy zinc to be in contact with thezinc rod. The zinc cell can be connected to a circulation pump thatdraws the solution from below the level of the zinc electrode and saltbridge and pumps it back into the top of the cell above the basketcontaining the mossy zinc. In addition, the argon enters at the verybottom of the cell and bubbles through any precipitated zinc chloride tomaintain the saturation point in the solution.

The carbide cell and zinc cell can be connected by a salt bridge, whichcan facilitate the flow of chloride ions from the zinc cell to thecarbide cell. The salt bridge can be comprised of two isolation valvesat either end, as well as a coupling which can hold an ion exchangemembrane, and a vent valve.

In some embodiments, the galvanic cell comprises an external powersupply.

The examples that follow demonstrate the use of reactions havingdifferent voltage potentials to produce different carbon allotropes andforms of the elemental carbon material.

WORKING EXAMPLES

Additional embodiments are provided by the following non-limitingworking examples.

Example 1

CaC₂+ZnCl₂→CaCl₂+Zn+C

An apparatus was constructed that included two glass cells connected bya glass tube. Along the glass connecting tube was a valve to isolate thetwo cells from one another and a glass fritted filter to prevent anysolid material from migrating between the cells. Each cell was roughlytwo inches in diameter and six inches high. The glass tube connectingthe cells was about 3 inches from the bottom or about in the middle ofthe vertical height of the cells. The cells also had a flat a bottom sothat they could rest on magnetic stirring plates to provide agitationduring the experiment.

Each cell was sealed with a glass cap using a glass ground joint andeach cap allowed for a ¼ inch tube to pass through the cap and extendinto the cell. One of the cell caps was equipped with an elemental metalelectrode (e.g., zinc or tin), while the second cell was equipped withan electrode which contains the carbide.

The caps for each cell were fabricated with a glass nipple roughly 5/16inch diameter. This permitted the elemental metal electrode from passingthrough the Into the cell. A 12 inch long, ¼ inch diameter elementalzinc rod was passed through the nipple on the cap of the metal cell. Apiece of Tygon tubing was slid over the top of the elemental zinc roddown to where it also covered a portion of the glass nipple in the cap.One hose clamp was placed around the Tygon tubing covering the nipplewhile another hose clamp was tightened on the Tygon tubing covering theelemental zinc rod. This was done in order to seal the cell and maintainan inert environment in the cell.

The carbide electrode was a hollow stainless steel mesh sphere with adiameter of 1 and ⅝ inches connected to a stainless steel tube. A smallhole was drilled in the side of the stainless steel tube within the cellto vent any vapors produced in the experiment. The other end of the tubethat was outside of the cell was connected to a valve using flexibleTygon tubing which was further connected to bubbler filled with methanolto prevent any oxygen or moisture from entering the cell.

The cells were prepared in the controlled environment of a glove box,free of oxygen and moisture. Several hundred milliliters of driedmethanol was prepared by removing the moisture dissolved in the methanolusing a molecular sieve. A magnetic stir bar was placed in each cell ofthe apparatus and the valve on the tube connecting the two cell wasclosed to isolate one cell from the other.

The first cell was filled with the dried methanol to a height of fourinches or one inch above the connecting tube. Zinc chloride anhydroussalt (ZnCl₂) was stirred into the dried methanol until the solution wassaturated. The cell cap, which was fitted with a ¼″ diameter elementalzinc rod was set in place using vacuum grease on the ground glass jointto seal the zinc cell. The bottom of the elemental zinc electrode wasimmersed in the ZnCl₂/methanol solution.

The second cell was also filled with the dried methanol to height offour inches or one inch above the connecting tube. Calcium chlorideanhydrous salt (CaCl₂) was stirred into the dried methanol until thesolution was saturated.

The calcium carbide (CaC₂) was then prepared by reducing the particlesize of the of the individual pieces to a size of less than onecentimeter. For this example, the calcium carbide was ground and crushedto a particle size between 3.5 and 14 mesh. Calcium carbide waspurchased from Acros Organics and the product name was Calcium Carbide,97+% (CAS: 75-20-7 and Code: 389790025). The calcium carbide was nottreated or purified before start of the experiment.

The CaC₂ was then sealed in the hollow stainless steel mesh sphere ofthe carbide electrode which had been fitted into the second cell cap.The carbide cell cap was set in place using vacuum grease on the groundglass joint to seal the carbide cell. The mesh sphere containing thecalcium carbide was completely immersed in the CaCl₂/methanol solution.Tygon tubing was connected to the opened end of the stainless steeltubing on the carbide electrode. A pinch valve was used to completelyseal the carbide cell from the environment.

The connected cells, which had been sealed and isolated from theenvironment, were removed from the controlled atmosphere glove box. Theconnected cells were set in place with the bottom of each cell restingon a separate magnetic stirring plate. The Tygon tubing connected to thetop of the stainless steel tube of the carbide electrode was connectedto the valve which was further connected to the vapor bubbler filledwith methanol. The pinch valve on the Tygon tubing was then opened tothe carbide cell. One side of a multimeter was connected to the zincelectrode and the other side was connected to the carbide electrodeallowing for the flow of electrons across the cells. The multimeter alsopermitted the voltage and current between the two cell to be measured.

The reaction took place at room temperature, which was estimated to beabout 23° C.-24° C.

The vent valve was opened between the carbide electrode and the vaporbubbler to allow any vapor produced to exit the carbide cell. Next, bothmagnetic stir plates were turned on to agitate the solution in each ofthe cells. Finally, the valve on the glass tube connecting the cells wasopened to allow for ions to flow between the two cells. The voltage andcurrent were measured using the multimeter to ensure that the reactionwas indeed proceeding.

After a period of time, the reaction was stopped by closing the valve onthe tube connecting the two cells.

The reaction time for Example One was about 28 hours.

The multimeter was disconnected along with the Tygon tubing attached tothe carbide electrode.

The carbide cell cap was removed along with the mesh stainless steelsphere containing the products of the experiment.

For describing the reaction products, two groups of products are noted.The first group is the product that remained inside the mesh electrode(“primary product”), and the second is the product that escaped the meshelectrode and was resting at the bottom of the glass cell (“secondaryproduct”). The primary and secondary products can be evaluatedseparately or they can be mixed and evaluated together in a mixture.

The products of the experiment were then removed from the mesh stainlesssteel sphere and treated with 6.0 molar hydrochloric acid (HCl) and thenflushed several times with distilled water.

The product at the bottom of the glass cells was the only productvisible prior to removal from the cell. In the cell immersed in thesolution, the product at the bottom of the cell appeared to be anoff-white colored gel. Small solid particles which were darker in colorcould be seen in the gel-like material. The first step in removing theproduct from the apparatus was to remove the glass cap with the meshstainless steel ball or carbide of holder from the cell. The holder wasopened up and its contents transferred to a 600 mL beaker filled with aone molar HCl solution. The contents of the holder had an appearance ofa light gray wet sand. The materials were transferred using a scapula.The remaining residual material was removed from the stainless steelholder using a spray bottle filled with the one molar HCl solution. Thecontents are also collected in the same 600 mL beaker. The cell wasemptied by first decanting off the supernatant solution. The remainingsolution along with the products at the bottom of the cell were pouredinto the 600 mm beaker containing the products from the stainless steelholder. The remaining residual material in the bottom of the cell wassprayed out into the 600 mm beaker using the spray bottle containing theone molar HCl solution.

After treatment with water and HCl the products had the appearance of afine gray powder, or more particularly, a darker gray powder.

The products of the experiment were confirmed to be only elementalcarbon using standard analytical methods including SEM and EDAX. Theatomic percent carbon was at least 98%.

A reaction product called “Sample A” is characterized in FIGS. 8-11. Theelemental carbon produced from the reaction described herein using zincincluded mainly two-dimensional carbon sheet or plates stacked on top ofone another which showed that the carbon was sp² hybridized. FIG. 8 (50micron scale bar) shows what the bulk material produced looks like,while FIGS. 9-11 are “zoomed in” portions of FIG. 8 (scale bars of fiveor two microns), to provide more definitive images of the plate-likestructure of the products.

The most striking difference between the SEM images from this Example 1reaction product compared to the reaction product of the elementalcarbon materials prepared by the thermal methods of PCT/US2014/028755was in the concentration of the amorphous carbon produced. In thisthermal method, much of the elemental carbon material product was of anamorphous nature, and it was difficult to see many interesting particlesof interest. See, for example, FIGS. 6 and 7. In the present Example 1,in contrast, it was immediately striking the amount of non-amorphouscarbon in the sample with many interesting particles of interest.

Another important difference is that in PCT/US2014/028755, the reactionof calcium carbide and zinc chloride was carried out at 425° C., a muchhigher temperature.

FIG. 17 shows the apparatus used in Example 1.

For product yield, 27.0 g of calcium carbide was added to the holder tobegin the experiment. Roughly 0.9 g of elemental carbon materials wasrecovered as a product. This amount of recovery was expected as thereaction was not allowed to proceed to completion. However, theobjective was met to show that elemental carbon material was producedusing the galvanic method at room temperature and pressure.

In Example 1, the average voltage was about 20 mV and the averagecurrent varied between about 0.5 and about 2.0 μA. Other thanfluctuating continuously, there was no real change in voltage andcurrent over the course of the reaction.

Example 2

CaC₂+SnCl₂→CaCl₂+Sn+C

For Example 2, which was based on tin chloride and tin rather than zincchloride and zinc, the apparatus was assembled in the manner describedin Example 1.

The cells were prepared in the controlled environment of a glove box,free of oxygen and moisture. Several hundred milliliters of driedmethanol were prepared by removing the moisture dissolved in themethanol using a molecular sieve. A magnetic stir bar was placed in eachcell of the apparatus and the valve on the tube connecting the two cellwas closed to isolate one cell from the other.

The first cell was filled with the dried methanol to a height of fourinches or one inch above the connecting tube. Stannous chlorideanhydrous salt (SnCl₂) was stirred into the dried methanol until thesolution was saturated. The cell cap, which had been fitted with a ¼″diameter elemental tin rod, was set in place using vacuum grease on theground glass joint to seal the zinc cell. The bottom of the elementaltin electrode was immersed in the SnCl₂/methanol solution.

The second cell was also filled with the dried methanol to height offour inches or one inch above the connecting tube. Calcium chlorideanhydrous salt (CaCl₂) was stirred into the dried methanol until thesolution was saturated. The calcium carbide (CaC₂) was then prepared byreducing the particle size of the of the individual pieces to a size ofless than one centimeter. The CaC₂ was then sealed in the hollowstainless steel mesh sphere of the carbide electrode which had beenfitted into the second cell cap. The carbide cell cap was set in placeusing vacuum grease on the ground glass joint to seal the carbide cell.The mesh sphere containing the calcium carbide was completely immersedin the CaCl₂/methanol solution. Tygon tubing was connected to the openedend of the stainless steel tubing on the carbide electrode. A pinchvalve was used to completely seal the carbide cell from the environment.

The connected cells, which were successfully sealed and isolated fromthe environment, were removed from the controlled atmosphere glove box.The connected cells were set in place with the bottom of each cellresting on a separate magnetic stirring plate. The Tygon tubingconnected to the top of the stainless steel tube of the carbideelectrode was connected to the valve which was further connected to thevapor bubbler filled with methanol. The pinch valve on the Tygon tubingwas then opened to the carbide cell. One side of a multimeter wasconnected to the zinc electrode and the other side was connected to thecarbide electrode allowing for the flow of electrons across the cells.The multimeter also permitted the voltage and current between the twocell to be measured.

The reaction took place at room temperature. The vent valve was openedbetween the carbide electrode and the vapor bubbler to allow any vaporproduced to exit the carbide cell. Next, both magnetic stir plates wereturned on to agitate the solution in each of the cells. Finally, thevalve on the glass tube connecting the cells was opened to allow forions to flow between the two cells. The voltage and current weremeasured using the multimeter to ensure that the reaction is indeedproceeding.

After a period of time, which was about 28 hours, the reaction wasstopped by closing the valve on the tube connecting the two cells. Themultimeter was disconnected along with the Tygon tubing attached to thecarbide electrode. The carbide cell cap was removed along with the meshstainless steel sphere containing the products of the experiment. Theproducts of the experiment were then removed from the mesh stainlesssteel sphere and treated with 6.0 molar hydrochloric acid (HCl) and thenflushed several times with distilled water. The products of theexperiment were confirmed to be only elemental carbon using standardanalytical methods.

The reaction products were determined to be clearly different from thereaction products of Example 1 and were mainly sp³ hybridizedallotropes.

The elemental carbon material reaction products are depicted in FIGS.12-16. The elemental carbon produced from the tin electrolysisexperiments included mainly of three-dimensional solid carbon particleswhich suggested that the carbon produced was sp³ hybridized. FIG. 12 isa larger scale image of the bulk carbon material produced by thisexperiment (scale bar, 100 microns). FIG. 13 is a magnified image of thematerial shown in FIG. 10 that allows the three-dimensional nature ofthe carbon to be identified (20 micron scale bar). FIG. 14 is an imagethat shows the 3D crystalline nature of the carbon produced (10 micronscale bar). FIGS. 15 and 16 are of the same particle at two differentscales (10 microns and 3 microns).

FIGS. 12-16 demonstrate that the products achieved were 3D structures,as opposed to the 2D stacked plates obtained in Example 1. The samplefrom which these figures were taken is called Sample B. Again, manyinteresting particles of interest were present in the SEM images.

In Example 2, a voltage of about 10 mV was generated along with anamperage of about 0.6 μA on average. Again, other than fluctuationsthere was no real change in the voltage or current.

Examples 1 and 2 employed galvanic cells that used the potential rangeof the reactions to determine which products could be produced in thatpotential range. The galvanic cells did not have a voltage source, butmerely measured the voltage that exists in galvanic cell during thereaction. The results demonstrate a voltage range that produces specificproducts, with each specific product being made at a specific voltagethat occurred during the reaction. Understanding the specific voltageassociated with each specific product can allow for the use of aelectrolytic cell, with the voltage controlled to the specific voltage,to produce a pure specific product.

To prove this, Examples 1 and 2 differed only with respect to theelemental metal electrode and cationic solution used, as well as thereaction products produced. As elemental zinc in a ZnCl₂ solution has adifferent chemical potential than elemental tin in a SnCl₂ solution, thegalvanic cells used in Examples 1 and 2 have very different cellpotentials. As such, the total voltage in the cell is different inExamples 1 and 2, creating different products. Products produced inExample 1 were more sp² hybridized, due to the specific range of cellpotentials produced by that reaction scheme. Products produced inExample 2 were more sp³ hybridized, due to the specific range of cellpotentials produced by that reaction scheme. Accordingly, Examples 1 and2 demonstrate that changing voltage, and, therefore, potential in theelectrolysis cell can specify the carbon allotrope products produced.

In each of the above Examples, the apparatus used did not include anexternal voltage source. Accordingly, the voltage between the cellsdecreased over time. This voltage change likely resulted in variation inthe produced material that, in theory, would not be experienced if thevoltage was maintained at a constant level.

Example 3

CaC₂+ZnCl₂→CaCl₂+Zn+C

In this experiment, a significantly larger apparatus was used comparedto that of Examples 1 and 2. The apparatus and items used to conduct theprocesses for Examples 3 and 4 are shown in FIGS. 19-23.

One day prior to the beginning of the experiment, methanol was dried andprepared for the reaction using molecular sieves to dehydrate thesolvent. The zinc electrode was then prepared by attaching the basket tothe zinc rod and filling it with “mossy zinc” (small nuggets of zincwith higher surface area made by rapidly cooling molten zinc in water).The zinc electrode and basket were then installed in the zinc cell byattaching it to the underside of the zinc cell lid. The containers ofzinc chloride were weighed and numbered to determine the weight of zincchloride used in the experiment.

The calcium carbide was prepared by weighing out four equal portions of250 grams each (1,000 g total) and placing them in sealed plastic tubsuntil the calcium carbide was loaded into the carbide electrode. Thevapor trap bubblers were filled with dried methanol to prevent any ofthe oxygen or moisture in the air from entering the cells of thereactor.

A basic cotton filter was inserted into the tube of the salt bridge toprevent solids from transferring across the salt bridge. The cottonfilter was used rather than the frit for convenience in scale up.

The carbide and zinc cells were isolated by closing the valves to thesalt bridge. All of the other valves were adjusted to load the solventinto the cells. The multimeter was connect to the carbide electrode andthe zinc electrode. The multimeter was then connected to a computerwhere the current and voltage can be recorded.

The container containing the dried methanol solvent was connected to thesolvent loading port for the carbide cell using a flexible PVC linedesigned to easily attach to the system and the carboy. The air to thecarbide circulation pump was turned on and the methanol was poured intothe system and pumped to the input at the top of the carbide cell. Oncethe desired level was reached, the pump was stopped and the containerdisconnected. The valves were adjusted and the pump was turned back onto begin circulating the solvent. The argon sparge was turned on tomaintain the inert atmosphere in the carbide cell.

Another container of the dried methanol solvent was then connected tothe solvent loading port for the zinc cell. The compressed air wasturned on to the zinc circulation cell and the methanol pumped into thecell through the top circulation port. Once the desired level ofmethanol was reached, the pump was stopped and the solvent loadingcontainer disconnected from the solvent loading port. The valves wereadjusted and the circulation pump was turned back on to circulate themethanol through the zinc cell. The argon sparge was turned on tomaintain the inert atmosphere in the zinc cell. The pressure of theargon feed was adjusted to the proper level at the regulator on theargon gas cylinder.

The solid calcium chloride was then added into the methanol of thecarbide reactor. 150 grams of calcium chloride was added to the solventof the carbide cell. The concentrated solution of CaCl₂ in methanol wasthen added to the carbide cell.

The carbide circulation pump and argon sparge flow rates were bothincreased to create additional agitation in the carbide cell and aid indissolving the calcium chloride into the methanol.

The zinc chloride was then added to the methanol in the zinc cell.Roughly 3.5 kilograms total of ZnCl₂ was loaded in the zinc cell for thereaction. The ZnCl₂ was poured directly into the top of the zinc cell.The zinc cell circulation pump and argon sparge flowrates were bothincreased to increase the amount of agitation in the zinc cell and aidin dissolving the zinc chloride into the methanol.

Next the salt bridge was filled with solution from each side and thesolids filter saturated which permitted ion flow. The carbide cellisolation valve was then opened and the solution was allowed to fill thesalt bridge to the solids filter. The vent valve was periodically openedto bleed off any of the air or argon trapped in the line. After severalminutes when the solid filter appeared saturated, the carbide cellisolation valve was closed. The zinc cell isolation valve was opened tofill salt bridge with solution on the zinc side of the solids filter.Once again, the valve was left open for several minutes and the ventvalve was periodically opened to bleed off any gases.

The calcium carbide was loaded into the carbide electrode. The flexiblecoupling that attaches the carbide cell lid to the rest of the cell wasloosened. The cell lid, flexible coupling, and carbide electrode werelifted from the cell up to a point where the bottom tray attached to theelectrode could be loaded. Four trays of 250 g of calcium carbide (1,000g total) were loaded into the respective locations.

The cell lid, flexible coupling, and carbide electrode were lowered backinto place and the coupling resealed to the top of the carbide cell. Theargon gas and circulation pump flowrates were adjusted to the desiredrates to begin the electrolysis reaction as described more below. Thedesired rates produced a nice, consistent agitation of the solution.

The multimeter was turned on and the voltage and current verified to beat zero. The chemical reaction was begun by opening the isolation valvesfor the carbide and zinc cells to permit the flow of ions across thesalt bridge. As the pure carbon production reaction and the undesiredsecondary reaction between the calcium carbide and methanol progressed,a portion of the reaction products exited the trays of the carbideelectrode in solid form. These solids eventually settled into theproducts of reaction trap at the bottom of the carbide cell. As theproducts of the reaction trap filled with solids, they were drained andthe carbide cell was refilled to the same level with the volume of driedmethanol that was removed.

The vent valve on the lid of the carbide was cracked open. The solids,along with a small portion of the methanol solution, were drained byopening the valve at the bottom on the carbide cell. The mixture wasdrained directly from the carbide cell into individual polypropylenetubs designed to be used in a large bucket centrifuge. Once the solidswere removed and the drain valve closed, the vent valve on the lid ofthe carbide cell was closed. Then the container of dried methanol wasconnected to the solvent loading port. An equal amount of dried methanolas was removed was added using the carbide circulation pump. Thecontainer of dried methanol was removed and all valves were properlyadjusted to once again circulate the solution.

The reaction was complete when the current reading from the multimeterdropped to zero. This indicated that the electron flow had ceasedbecause all of carbide had been consumed or there was not enough contactbetween the remaining pieces of carbide and the electrode to sustain acurrent flow. Once the reaction stopped, the solution and anyaccumulated solids were drained out of the carbide cell into theindividual centrifuge tubs at 750 ml per tub. Each tub was centrifugedwith the liquid solution decanted and collected for further solventrecovery operations and the solids containing the pure carbon productremained in the centrifuge tub to begin the cleaning and separationprocess. The decanted liquid was stored in one gallon containers whichwill be further processed in the distillation column. During this time,the carbide cell circulation pump continued to run and wash any solidsfrom the cell walls, electrode, and the surface of the unreacted carbideto be removed with the liquid solution.

After the carbide cell was drained, the flexible coupling at the top ofthe cell was loosened. The lid was raised from the cell and the bottomportion of the electrode containing the carbide was removed. Anyunreacted carbide was collected and weighed for mass balancecalculations. An acid solution was then applied to clean out the insideof the reactor. Then a small amount of the solvent for the nextexperiment was circulated through the cell to rinse any of the acidsolution away and absorb any water molecules present from the mild acidsolution.

The drained material was placed into a centrifuge tub. The centrifugetub was then centrifuged in the large bucket centrifuge at a speed of3500 RPM for ten minutes. The solids formed a cake at the bottom of thecentrifuge tub and the liquids were decanted off to be further processedin the distillation column. The remaining solids were treated with a 3.0molar HCl solution. The HCl was allowed to react with the reactionproducts on a stir plate providing agitation overnight. The solution wasthen centrifuged.

The solids were then further treated with a stronger HCl solution of 6.0M. The acid treatment was allowed to proceed for 24 hours. The acidtreatment was repeated three times. The remaining solids weretransferred from the centrifuge tub into a fine particle size glassfitted using distilled water and mild acid solutions. The glass fittedfilter was placed on top of a vacuum flask with a gasket and attached tothe house vacuum system to pull the water and methanol flushes throughthe material and filter. The residual salts were rinsed away bycontinual flushing of the product with distilled water and methanol. Thefinal flush was performed with methanol so that the product wascompletely dried before it was removed from the filter and weighed formass balance.

The reaction solvent was recovered by distilling the solution drainedfrom each of the cells. After centrifugation, the methanol/calciumcarbide solution was collected. A portion was loaded into the boilingpot of a distillation column. The solution was heated to a point thatthe solvent was evaporated from the solution and further condensed andrecovered in the collection flask. The remaining concentrated calciumchloride solution was dried to solid calcium chloride and discarded.Calcium chloride was generated by the process.

Once all of the methanol/calcium chloride solution was distilled, themethanol/zinc chloride solution was then distilled. The solvent wasevaporated from the solution and recovered in the collection flask.

14.6 grams of pure carbon product was recovered (3.9% yield of carbon).Some the carbon was unreacted and removed as acetylene in the cleaningprocess. Other carbon was reacted with the methanol in the undesiredsecondary reaction.

The time of the reaction was about 15 days.

The elemental carbon product from Example 3 was examined by SEM and EDAXand Raman spectroscopy. Stacked plate-like structures were observed. Insome cases, the diameter or lateral dimension of the stacks weredecreasing continuously so that an exfoliation process should providegraphene plates of different diameters or lateral dimensions. See FIGS.24-27.

Example 4

CaC₂+ZnCl₂→CaCl₂+Zn+C

In Example 4, the procedures of Example 3 were generally repeated.However, several changes from the procedures of Example 3 were madeprior to the start of the experiment.

The first was that the methanol in the vapor trap bubblers was replacedwith vacuum pump oil to prevent evaporation and maintain the barrierbetween the inert atmosphere of the reactor and the atmosphericconditions inside the laboratory. The second change to the apparatus wasto remove the solids filter in the salt bridge and replace it with moresubstantial solids filters. Instead of the loose cotton filter, twodiscs were cut from a sponge to fit snugly inside of the connectiontube. The loose cotton was then compressed between the two discs whichcompletely prevented the migration of the solids from the carbide cellto the zinc cell. Once the reaction began, there was no observabledecrease in the current from the initial experiment.

The methanol was replaced with vacuum pump oil in the vapor trapbubblers because the methanol can evaporate overnight and the barrierbetween the inside of the reactor and the atmosphere can be broken. Asdescribed below, the more substantial solid particle filter was added tothe salt bridge to better prevent solid material from migrating from onecell to the other.

Additionally, the solid calcium chloride was dissolved in dried methanolbefore introducing it into the carbide cell.

After the reaction was stopped and the carbide cell drained, the carbideremaining in the electrode was removed and processed to determine ifthere was any pure carbon product retained in the carbide. The remainingcarbon products on the carbide were removed.

The carbide cell circulation piping was also connected to the vapor ventvalve on the salt bridge. When the solids were flushed from the saltbridge there was no change to the current or voltage of the systemfurther indicating that the temporary change of flow did not affect thereaction. The electrolysis reaction was stopped after 17 days.

19.1 grams of pure carbon were recovered (5.1% yield for carbon).

The elemental carbon product from Example 4 was examined by SEM and EDAXand Raman spectroscopy. Stacked plate-like structures were observed.Hexagonal structures and flat surface structures were observed. SeeFIGS. 28-31.

FIG. 32 is also an SEM image (scale bar, 50 microns) produced fromExample 4. It is a composite particle of elemental carbon orgraphene-like plates. It appears to be a fused together particle ofsmaller individual hexagon shaped stacks of graphene-like plates.

Example 5

CaC₂+ZnCl₂→CaCl₂+Zn+C

This example was carried out using the same apparatus as used inExamples 3 and 4 with the exception being the solvent used in thereaction. The methanol used as the solvent was replaced with ethanol.Ethanol reacts with the CaC₂ at a much reduced rate relative to reactionof methanol with CaC₂. However, the solution of the salts in ethanol isless conductive than in methanol and, therefore, the rate of the desiredelemental carbon producing reaction was also reduced. Because of thedecreased reaction rate, the reaction time of Example 5 was allowed toproceed for 27 days which produced some large particle size pieces ofelemental carbon material.

After the reaction portion of Example 5 was complete, it was discoveredthat an undesired zinc hydrate material was dissolved in the solvent ofthe carbide cell. When water was added, the undesired materialprecipitated out of solution and produced a gel-like material. Thisundesired material complicated the cleaning process. In addition, a morerigorous cleaning produced was used to ensure that most, if not all, ofthe contaminants were removed. Furthermore, the material produced wasclassified into a fine, middle, and large cut based on a need to producesmaller particle size product for a characterization analysis.

Summary of the Cleaning Process for Example 5:

After the reaction was complete, the valve on the salt bridge was closedisolating the two cells. Roughly 3 liters of the solution from thecarbide cell were drained into six separate centrifuge tubs for thelarge bucket centrifuge. The solution was centrifuged no solid materialwas forced out of solution. Water was then added to the first time and amaterial precipitated immediately. This was later identified as a zinchydrate compound. This undesired zinc hydrate precipitated immediatelyupon contact with water and was very difficult remove and separate fromthe other products of reaction. The goal would be to isolate the productfrom the solution before it has a chance to precipitate. This was doneby first decanting off the solution from the products of reaction. Driedethanol was immediately used to immerse the products so any residualsolution would not react with the moisture in the air and form theundesired zinc hydrate material. This action was repeated several timeswith dried ethanol in order to dilute and flushed away any of theresidual solution and eliminate the formation of the undesired zinchydrate.

The zinc hydrate did form to a small extent due to short exposure timesto the air. The only thing it had responded to is concentrated or 13.0 Mhydrochloric acid. The effort was made to use only the standard cleaningand separation chemicals to deal with this undesired material. The nextstep was to dissolve away any of the unreacted calcium carbide. Based onthe material remaining, there was a large amount of the calcium carbideleft unreacted. Acid solutions were mixed with the unreacted products ofreaction to react away the calcium carbide. This treatment also removeany residual salts. The remaining product is a high percentage ofelemental carbon greater than 90%.

Additional operations were performed in order to further remove anyresidual materials or contaminants an increase the percentage ofelemental carbon and the product. Operations were also performed toseparate the product into three distinct particle size cuts. Theremaining products are separated into several different beakers. Severalmore rinses were performed with HCl. The supernatant liquid was decantedthrough a 4.5-5.0 μm glass fitted filter. After several additional acidtreatments, the products of reaction were then split into only a fewbeakers and the products immersed in dried ethanol. These beakers wereplaced in the ultrasonic bath and left for several hours. The beakerswere removed from the ultrasonic bath and placed on stir plates forroughly 10 minutes. The beakers were removed from the stir plate andallowed to sit for a length of time and allow the product to settle outof solution based on and particle size. The supernatant liquid was thendecanted through the glass fitted filters. The solids retained by thefilters were then separated and collected representing the fine particlesize cut of the product. This action continued numerous until theproduct was sufficiently cleaned and separated into three distinctparticle sizes.

The procedures below describe in more detail various cleaning andclassifying procedures for this experiment.

Rigorous Cleaning and Classifying Procedure:

The process of cleaning the carbon produced in Example 5 was complicatedby the formation of a zinc hydrate material as an undesired product.This phase of the experiment in Example 5 started with all of productdistributed between five one liter beakers and one larger three gallonbucket with lid.

The three gallon bucket contained all of the solvent drained from theelectrolysis reactor where the solvent also contained the small particlesize (fine) carbon material. The bucket was left undisturbed for severaldays allowing the fine carbon to settle out of solution. Normally, thefine carbon would be separated out of the solvent using a largecentrifuge. But for this experiment, the enhanced gravity of thecentrifuge was unable to force the solids from the solution. From pastexperiments, it was learned that that fine material that could not berecovered via centrifugation would eventually settle out of solution ifleft undisturbed.

The five one liter beakers contained all of the solid product thatremained in the solid contained in the baskets of the carbide electrode.They also contained all of the other non-carbon material from theelectrolysis reaction after the unreacted carbide was treated with oneconcentrated HCl treatment. The solutions in the beakers also containany of the undesired zinc hydrate material remaining from the reaction.The first objective was to separate and recover the maximum amount ofproduct in most time efficient method possible so the product could betreated with HCl for a second time with all (or the vast majority) ofthe undesired zinc hydrate material finally removed.

The apparatus used for separating the solid product from the solutionwas a fine particle size (4.0-5.5 micron) glass fritted filter placed ontop of a two liter vacuum flask. A gasket was place under the filterusing vacuum grease to seal it to the vacuum flask. The flask wasconnected to the house vacuum system to pull a vacuum inside of theflask which, in turn, pulls the liquid and ions in solution through thefilter leaving a solid that had a much greater concentration of purecarbon product.

1. Set-up of the Equipment to Perform the Cleaning/Separation:

Prior to setting the filter/vacuum flask apparatus, the glass frittedfilters were all thoroughly cleaned to provide an opened filter for thegreatest flow rate of the solution through the filter. This wasaccomplished by cleaning the filter with the laboratory glass cleanerand then placing the filters in the furnace overnight at 500° C. in anoxidizing environment which reacts any material entrained in the filterto produce ash. The underside of the filter was then subject to vacuumand flushed with methanol to rinse any of the now smaller particle sizeash out of the glass fitting.

Cleaning the glass fitted filters using this cleaning/oxidation/rinsingmethod were performed on a regular basis at the end of each day whilepreviously cleaned filters were rotated in. This increased theefficiency of the filtering process by maintaining as high of flow ratethrough the filters as possible given the situation.

Four of the filter/vacuum flask system were set up and filtering processto begin the filtering process from the first HCl treatment. Theundesired zinc hydrate material forms a gel like substance. The gelsettles on the surface on the glass fitted filter which partially orcompletely blinds the filter. A blinded filter means that something (thezinc hydrate gel) is preventing or greatly restricting the solution frombeing pulled through the filter. This is why it was so important tofinally remove all of the zinc hydrate and allow the product to beproperly cleaned. The solid product is also pulled to the surface of thefilter which also acts to blind the filter.

Two of the four filter systems were started, and as expected the flowrate through the filters was very low, only a drop or two every fewseconds. One way to increase the rate of transfer through the filter wasto continually move the blinding material from the glass fritted surfaceusing glass stirring rod or rubber laboratory spatula. An additionaloption is to add concentrated HCl (the other chemical use on a regularbasis in the process which dissolved the zinc hydrate gel) directly tothe filter. But this method is only effective for the filter blindingdue to the gel and does not help with blinding from the fine productmaterial in the filter.

One goal was to isolate smaller particle graphene materials (under 20microns) for further testing in products. Therefore, another object ofthe cleaning and separation procedure is to separate the product byparticle size and supply the finer cut of the carbon for product testingof Example 5 product. So in addition to cleaning and purifying theproduct, the next few steps will begin the process of separation byparticle size.

In addition to separating out the finer carbon for further producttesting, the particle size separation is important for Example 5 becauseit appears that there are several pieces of very large product. Anotherobject was to separate out the very large pieces (on the scale of one totwo centimeters) for further evaluation and analysis to control betterthe growth mechanism of the pure carbon product using the electrolysisreaction.

Two additional one liter beakers were used to decant off the supernatantliquid containing a smaller amount of the fine carbon product. Smalleramount means the percentage of solids per volume of supernatant liquid.

Any of the solids leaving the beaker with the decant solution willinclude the smaller particle size carbon material. Since the product ismostly pure carbon at this point the specific gravity for the solidsshould be fairly consistent. This means that the settling rate of thematerial is controlled by the particle size. The smaller the particle,the smaller percentage of the forces acting on it will be gravity.Therefore, as settling time increases, smaller and smaller particle sizesolids will remain suspended in the solution.

2. Processing the Gel-Like Clumps of Material:

Several of the beakers contained a large ‘clump’ of the gel suspended inthe supernatant liquid which also had product entrained. These clumpswere decanted one at time into the first of the one liter decantbeakers. Once the clump was isolated in the beaker it was treated withadditional concentrated HCl and agitated for as long as need to dissolvethe undesired zinc hydrate clump.

Once dissolved, the contents of the first decant beaker were added tothe filter and the solution allowed to be separated away. The filtersonly hold a maximum of 150 ml so the contents of the beaker werecontinually added during filtration until the entire contents of thebeaker were filtered.

Any of the residual material remaining in the beaker was transferred tothe filter using methanol. Furthermore, the solids were flushed severaltimes (between 2-4 times) with methanol to remove impurities from thesurface of the material prior to the second acid wash. It was importantto use methanol instead of distilled water because water can react toform additional small amounts of the gel substance.

After the material was dried from the vacuum, it was transferred intothe fine carbon collection beaker using the spatula and methanol. Thisfine carbon beaker also contained concentrated HCl for the second acidwash. The filter was put aside to be cleaned and oxidized while a fresh,cleaned filter was sealed to the vacuum flask to process the nextdissolved ‘clump’ of gel-like material containing solids.

The steps in this section were repeated until all of the ‘clumps’ of thegel like material have been processed and the product recovered for thesecond acid treatment.

3. Processing the Supernatant Decant Solution and the Products itContains:

In addition to processing the gel-like material, the rest of thesupernatant liquid containing the finer particle size carbon product wasbeing processed simultaneously. This section of the cleaning/separationprocess requires the largest volume of the supernatant liquid to beprocessed which is the most time intensive part of the filtration due tothe partial blinding of the glass fitted filters. So the main object forthis step was to recover the maximum amount of solid product whileremoving most if not all of the undesired zinc hydrate in the most timeefficient method.

The second decant one liter beaker was used and a third decant beakerwas added. This step began by decanting the supernatant while finesolids from the five original beakers. All of the beakers that did notcontain any of the gel like clumps were decanted into the second decantbeaker and allowed to sit overnight for the solids to settle.

After the ‘clumps’ where removed from the other beakers, they were thendecanted into the third decant beaker the following day and allowed tosettle overnight. The large clumps were not in this step, but theundesired zinc hydrate was still present in the solution so the filterblinding from the gel was still a problem. But main factor in the flowrate through the filter was now the blinding due to the fine particlesize solids. This is why the decant beakers were allowed to settleovernight. Much of the supernatant solution could be processed throughthe filters with only minimal amount of the solid product available toblind the filter.

After the solids had settled, the solution was continually added to thefilters. This step processed at a reasonable rate as long as themajority of the solids were retained in the decant beakers but stilltook several days to complete. The blinding was managed in the samemanner as the previous step where the filter surface was exposed using aglass stirring rod and rubber spatula. Concentrated HCl was also addeddirectly to filter to dissolve any the gel like material forming on thesurface of the filter.

Due to the volume of solution, there were several instances where thefilter became totally blinded, meaning that the flow rate through thefilter dropped to zero. In this case, the contents of the filters weretransferred back into the decant beaker using methanol and allowed tosettle. A clean filter replaced the blinded filter and the processcontinued. The blinded filter was cleaned and oxidized to be used later.

This step proceeded by processing one of the decant beakers while theother was used to collect material as to allow the solids to settle. Thenext day, the settled beaker was processed.

Once the volume of the filter was filled with anywhere between 10%-40%with solids (depending of the flow rate of solution through the filter),the solids were flushed several times with methanol to remove anyresidual material from the surface of the material. The solids wherethen transferred in the fine carbon beaker along with the material fromthe ‘clumping’ process step to wait the second acid treatment.

The steps in this section were repeated until all of the decantedmaterial was processed.

4. The Second HCl Acid Treatment and Alcohol Rinses of the Fine CarbonProduct:

Once all of the decanted products where processed into the fine carbonbeaker, it was filled with concentrated HCl, agitated on a magneticstirring plate, and allowed to react for 40 hours.

After the HCl treatment, the solids were allowed to settle overnight tominimize the time required to filter the large volume of liquid.

The entire contents of the fine carbon beaker were filtered using thesame methods as the previous steps using multiple filter/vacuum flasksystems.

Once the solid material was mostly dried from the solution in thebeaker, it was flushed and agitated in the filter with roughly 100 ml ofmethanol anywhere between 8-12 times. This removed most if not all ofthe impurities from the surface of the pure carbon products.

After the fine carbon product solids had dried in the filter undervacuum, it was transferred into a 600 ml Berzelius tall form beaker foradditional cleaning and refining steps. At this point, the fine cutshould only contain the pure carbon product with trace amounts ofimpurities, most of which may be trapped in between the stacked sheetsof graphene.

5. Processing the First HCl Acid Treatment of the Coarse Carbon Product:

The coarse, or larger particle size cut, of the pure carbon product isstill contained in the five original one liter beakers immersed in avolume of the solution just great enough to cover the solid material. Atthis point, most of the mass of product is contained in this coarse cutin the five separate beakers. Although much of the material needs tostill be filtered from the first HCl treatment, the time required shouldbe about the same since there is much less supernatant liquids that mustpass through the glass fritted filter. In addition, the particle size ofthe solids is greater, so the blinding due to the solid material shouldbe less of problem than with the finer cut of the solid product.

The solids, along with the supernatant liquid, were transferred into afilter. Methanol was used if needed to transfer any of the material fromthe beaker into the filter. The volume of the filter is filled between30%-40% with solids and the supernatant allowed to separate through thefilter.

After the material in the filter had partially dried, it was flushed andagitated with roughly 100 ml of methanol and allowed to filter. Themethanol flush was repeat between 3-4 times. At this point the solidshould contain a high concentration of pure carbon material.

The solids where transferred from the filter into a clean one literbeaker to await the second HCl treatment.

All of the remaining solids in the five original beakers were processedusing this method. The volume of material was large enough that two oneliter beakers were needed for the second HCl treatment of the coarse cutof the carbon product.

6. The Second HCl Acid Treatment and Alcohol Rinses of the Coarse CarbonProduct:

The two beakers containing the coarse cut of solids from Example 5 werefilled with concentrated HCl, agitated on a magnetic stirring plate, andallowed to react for roughly 40 hours.

After the HCl treatment, the solids were allowed to settle overnight tominimize the time required to filter the large volume of liquid.

The entire contents of the coarse solids beakers were filtered using thesame methods as the previous steps using multiple filter/vacuum flasksystems.

Once the solid material was mostly dried from the solution in thebeaker, it was flushed and agitated in the filter with roughly 100 ml ofmethanol anywhere between 8-12 times. This removed most if not all ofthe impurities from the surface of the pure carbon products.

After the fine carbon product solids had dried in the filter undervacuum, it was transferred into a single one liter Berzelius tall formbeaker for addition cleaning and refining steps. At this point, thecoarse cut should only contain the pure carbon product with traceamounts of impurities, most of which is probably trapped in between thestacked sheets of graphene.

7. Sonication Treatment and Settling Rate Separation of the Pure CarbonProduct from Example 5:

Sonication is the method of applying sound energy to a system, in thiscase applying sound energy to a beaker filled with a solution containingsolid particles including stacks of two dimensional sheets. Sonicationis a widely used method of agitating and dispersing solutions containingsolid particles. It is also a technique used to disperse commerciallypurchased graphene, which arrives as large pieces of agglomeratedgraphene sheets. This agglomeration is normal as the graphene sheetsdry.

For the Example 5 cleaning and separation process, the solids in thefine particle and coarse particle beakers were immersed in methanol andthe beakers suspended in a Cole-Parmer 8854 Ultrasonic bath. In additionto dispersing the solids, it is believed that the ultrasonic energy withsolids immersed in the low surface tension methanol will allow theliquid to penetrate the areas between the graphene sheets to a greaterextent. The penetration of the methanol between the graphene sheets willdissolved and remove more of the calcium ions and other impuritiesremaining in the final carbon product.

Another possible advantage of the sonication treatment of the product isthe exfoliation of the graphene sheets. There has also been researchinto graphene exfoliation using various solvents. So it was expectedthat exfoliation during the sonication treatment will occur but it wasunclear to what extent exfoliation will occur. If the graphene sheetsare exfoliated, then removing any impurities from between the sheetswhile they are stacked will become much more effective and efficient.Furthermore, exfoliated graphene can be laid down as a film, and thequality of the material produced can be more accurately assessed.

In addition to the sonication treatment, the solid material was alsoseparated by particle size during this section of the process. When thebeakers were removed from the ultrasonic bath, they would be agitatedusing a magnetic stirring bar. The agitation would be stopped and thesupernatant liquid with suspended solids would be decanted into a beakeror directly into the glass fritted filter. There was usually a briefamount of time (no more than a few minutes) to allow for the largerparticles to settle out of the supernatant solution. During the fewmoments of settling, any larger particles that were suspended in thesolution during agitation settled to the bottom of beaker before thesmaller particles which stayed suspended for a long period of time.Therefore, the solid particles suspended in the supernatant solutionwould be the smallest particle size material on average. This is how theparticle size separation for the carbon material produced wasaccomplished.

The following is the procedure used for sonication treatment andparticle size separation of the solid material from Example 5:

Both the fine particle size and coarse particle size beakers weresuspended in the ultrasonic bath. By suspended in the bath, they wereheld in place using an adjust laboratory clamp. The beakers were filledroughly half way with methanol.

During the first day, the ultrasonic bath was allowed to run for onehour. The beakers were periodically agitated during this hour torearrange which solid particles were closest the glass surface of thebeaker or closest to the source of the sonic energy.

The beakers were removed from the ultrasonic bath, dried off, and placedon magnetic stirring plates. The solid particles were agitated for 10-15minutes. The beakers were then removed from stirring plates and placedback into the ultrasonic bath for another hour. This process wasrepeated several times for an entire day.

At the end of the day, the beakers were placed in the hood and the solidparticles allowed to settle overnight.

The next morning, the supernatant liquid which contained almost nosolids was decanted into two separate filters, one for the fine particlesize carbon and one for the coarse particle size carbon.

The beakers were filled about half way with methanol and place in theultrasonic bath for further sonication treatment.

At this point, the treatment of the two beakers diverges. Both beakersof material will still continue to receive sonication treatments, butthe smaller particles suspended in the supernatant liquid of the coarsesolid beaker will be decanted prior to allowing the particles to settleout of solution. The decanted solid particles of carbon product from thecoarse beaker will then be filtered and flushed with methanol beforebeing added to the fine particle beaker for continued processing. Thisprocess allows the smallest carbon particles (on average) from thecoarse portion of the product to be removed and added to the fineportion of the product. The separation will not be perfect, but themajority of the finest carbon product will be contained in the fineparticle beaker.

After one hour in the ultrasonic bath, the coarse beaker was removed andplaced on the stirring for several minutes. The coarse beaker was thenremoved and allowed to settle for several additional minutes.

The solids and supernatant liquid were then decanted into the filter.The liquid was to transfer through the filter leaving behind the solids.

Once the solids in the filter were partially dried from the vacuum, theywere flushed 3-4 times with methanol to remove any residual contaminatesfrom the surface.

After the fine cut of solids from the coarse beaker were flushed, theywere transferred into the fine particles beakers.

The decanted coarse beaker was then partially filled with methanol andplaced back in the ultrasonic bath. The sonication energy continued todisperse the solids allowing the smaller particles to become suspendedin the solution. These particles can continue to be separated out untilthe smallest particle size material is transferred from the coarseparticle beaker into the fine particle beaker.

This process is continued until the agitated particles in the coarsebeaker settled out of solution very quickly (almost immediately). Thisindicated that the smallest particle size solids have been removed fromthe coarse cut of the product into the fine cut of the product.

The objective behind this separation technique was to generate areasonable amount of pure carbon product mostly of the finest particlessize. This was to prepare a fine particle size product for furtherproduct testing consisting of material subject to an extensive cleaningprocess to remove contaminates.

Over the several days of the particle size separation, the fine particlebeaker continued to receive sonication treatment.

Every 2-3 hours the fine solids beaker was removed from the ultrasonicand allowed to settle for roughly 15 minutes.

The supernatant liquid was decanted into a filter/vacuum set-up. Afterthe liquid was removed, any solids were flushed several times withmethanol and then added back to the fine particle beaker for furthersonication treatment.

When the particle size separation was complete, the entire contents ofthe fine particle size beaker were transferred the several filters. Ineach of the filters, the fine particle size carbon product was flushedseveral time with methanol and allowed to dry from the vacuum.

Once the solids in the filters were dry, they were placed inside in thedrying oven at 105° C. to drive off any remaining methanol or othermoisture.

When the product was completely dried, the filters were removed from thedrying oven and allowed to cool.

The product was weighed and transferred to a Fine Particle Size CarbonProduct sample container.

Characterization of the large piece of product of the elemental carbonmaterial reaction product is further shown in FIGS. 33-45.

FIG. 33 shows a comparison between the very large piece of Example 5 andcommercial graphene of much smaller size.

FIG. 34 is a first SEM image showing a top view of a large piece ofcarbon product (Sample C) (scale bar, 200 microns). FIG. 34 shows amagnified image of a piece of large graphene produced in Example 5. Theimage shows the edge of the solid piece that extends beyond the range ofthe image. It also shows a fragment of a hexagon shaped piece ofelemental carbon. It is typical to find elemental carbon hexagons with across-sectional area of roughly 50 μm. This is roughly thecross-sectional area of the fragment seen in the picture and is usedalong with the edge of the piece to give a representation of the largescale of this carbon piece in an SEM image.

FIG. 35 is a second SEM image showing Sample C with a perspective view(scale bar, 200 microns).). FIG. 35 shows the edge of the elementalcarbon piece seen in FIG. 34. With the naked eye, one could see that thelarge elemental carbon pieces produced in Example 5 had a twodimensional shape. FIG. 35 shows the edge or the depth of the twodimensional piece. It also shows that the solid piece appears to be madeup of individual sheets of elemental carbon or graphene.

FIG. 36 shows Raman spectra for Sample C. These are Raman spectragenerated from different samples all overlaid on top of one another. TheG peak and the 2-D peak are roughly the same height. This is uniquebecause other Raman spectra observed for material produced using thisprocess produces a Raman spectra where the G peak is a good deal higherthan the 2-D peak. This indicates that for this sample in Example 5 thesample is thinner on an atomic level in the third dimension and thatthis material has different characteristics from the other materialsproduced using this galvanic cell technology.

FIG. 37 is an SEM image showing Sample C and material morphology withincrevices (scale bar, 40 microns). FIG. 37 is a magnified image of FIG.35. FIG. 35 appears to show several (two or three) composite layer madeup of smaller layers. In between the larger layers of FIG. 37 there aregraphene hexagons contained within the gap. These hexagons have the verycommonly seen cross-sectional particle size of roughly 50 μm.

FIG. 38 shows an optical micrograph for top view of Sample C (scale bar,390 microns). FIG. 38 shows an optical image of the overall large carbonpiece. From this image, it can be clearly seen that this is not tinygraphene flakes (on the order of single microns or tens of microns)coagulated together because it has dried and was not in solution. Italso shows the overall size of the elemental carbon particle given thescale bar on the bottom right of 390 microns.

FIG. 39 shows an optical micrograph for perspective view of edge ofSample C (scale bar, 240 microns). FIG. 39 shows the same graphene pieceas in FIG. 38. However, in FIG. 39, the angle of the optical image isrotated from perpendicular so the third dimension can be observed. Thisimage further shows the stacked two dimensional nature of the largegraphene particle.

FIG. 40 is an SEM image showing Sample C (scale bar, 30 microns). FIG.40 shows an image of elemental carbon produced from Example 5. FIG. 41is a magnified image of the same piece of carbon. The most interestingthings about these two SEM images are the tiny fin like projections fromthe surface. In FIG. 41, it is also interesting to look at theorientation of the overall particle. Some of them appear to beperpendicular to one another while some of them appear to be at fairlyconsistent angles.

These images, and other images shown herein, show evidence of specificelemental carbon materials and graphene materials that can be producedusing this technology.

In addition, in FIGS. 42-45, comparative examples are shown fordifferent scale bars between the elemental carbon materials from theprior thermal methods (U.S. application Ser. No. 14/213,533 and PCTApplication PCT/US2014/028755) compared to Example 5.

Example 6

The same basic set up as Examples 1 and 2 with the small glass reactorshown in FIG. 17 was used for this experiment. However, there are threemajor differences between Examples 1 and 2 and this example. The firstis that the anode and cathode in the reaction were both connected to apotentiostat which applied an external voltage to the reaction system.The applied external voltage would in turn alter the chemical potentialof the reaction. The second major difference was in the apparatusitself. The glass caps which held the two electrodes were replaced bylarge rubber stoppers. This change was made because it was moreeffective in sealing the reaction environment and also permitted fordifferent setups to be quickly changed and altered between experiments.For example a glass caps in Examples 1 and 2 could not accommodate areference electrode. A simple alteration of the rubber stoppers wouldallow for either cell to accommodate the reference electrode or anyother item needed to perform the experiment. The third major differencewas that ethanol was used as the solvent in this experiment as opposedto methanol which was used in Examples 1 and 2.

A new anode was fabricated identical to the anode used in Examples 1 and2. They included a spherical tea ball strainer supported by a rod whereone face rotates to seal the strainer. This strainer included a carbonsteel with a stainless steel coating. It was selected for initialexperiments because it easily met the requirements of the experiment.These requirements were to hold the carbide and provide an electricallyconductive surface and had a greater resistance to corrosion than carbonsteel. A quarter inch 316 stainless steel rod was connected to the teastrainer with a hole was drilled in the side to vent any pressure buildup in the carbide cell. The stainless steel rod passed through therubber stopper and supported the anode within the cell. The top of thetube was connected to bubbler which provided a separation between thereaction environment and the environment in the lab.

The first cell was filled with the dried ethanol to a height of fourinches or one inch above the connecting tube. Zinc chloride anhydroussalt (ZnCl₂) was stirred into the dried ethanol until the solution wassaturated. The cell cap, which was fitted with a ¼″ diameter elementalzinc rod was set in place using vacuum grease on the ground glass jointto seal the zinc cell. The bottom of the elemental zinc electrode wasimmersed in the ZnCl₂/ethanol solution.

The second cell was also filled with the dried ethanol to height of fourinches or one inch above the connecting tube. Calcium chloride anhydroussalt (CaCl₂) was stirred into the dried ethanol until the solution wassaturated.

The calcium carbide (CaC₂) was then prepared by reducing the particlesize of the individual pieces to a size of roughly one centimeter.Calcium carbide was purchased from Acros Organics and the product namewas Calcium Carbide, 97+% (CAS: 75-20-7 and Code: 389790025). Thecalcium carbide was not treated or purified before the start of theexperiment.

The CaC₂ was then sealed in the hollow stainless steel mesh sphere ofthe carbide electrode which had been fitted into the carbide cell cap.The carbide cell cap was set in place into the ground glass joint toseal the carbide cell. The mesh sphere containing the calcium carbidewas completely immersed in the CaCl₂/methanol solution. Tygon tubing wasconnected to the opened end of the stainless steel tubing on the carbideelectrode. A pinch valve was used to completely seal the carbide cellfrom the environment.

The cap for the cathode cell was prepared with two openings. The firstopening was in the center of the cell and held the elemental zinc rodwhich was immersed in a solution of dried ethanol and zinc chloride. Thesecond opening was roughly half way between the center of the cell andthe wall. This opening held the Ag/AgCl₂ reference cell where the tipwas also submerged in the solution. The anode, cathode, and referenceelectrodes were snugly fit in and sealed in the holes of the rubberstopper for the cell caps.

Once both cells have been sealed and the electrodes in place, thepotentiostat and an amp-meter were connected in series between the zincand CaC2 electrodes. The potentiostat was a Bioanalytical Systems Inc.(BAS) Power Module model PWR-3.

The vent valve was opened between the carbide electrode and the vaporbubbler to allow any vapor produced to exit the carbide cell. Next, bothmagnetic stir plates were turned on to agitate the solution in each ofthe cells. Finally, the valve on the glass tube connecting the cells wasopened to allow for ions to flow between the two cells. The voltage andcurrent were measured using the multimeter to ensure that the reactionwas indeed proceeding.

The reaction that is expected to occur is:CaC₂+ZnCl₂→2C+CaCl₂+ZnIn this reaction, Zn⁺² is reduced to elemental zinc. The carbide anionis oxidized to elemental carbon. The standard reduction potential ofeither half-cell is not known in ethanol. It has been observed that thisreaction occurs spontaneously at room temperature.

With an applied potential of 0V, a current of 5 uA was measured. Avoltage of 14V was applied. The current increased from 5 uA to 100 uA.This is significant, as it implies an increase in reaction rate. Thezinc cell became clear as the reaction progressed, implying that thezinc chloride was consumed. More zinc was added, until there wasundissolved zinc chloride in the cell. The current increased to 150 uA.As the reaction continued, the current steadily increased to 200 uA.This is probably from the formation of calcium chloride in the calciumcell. The production of calcium chloride would increase the conductivityof the electrolyte. The reaction was allowed to continue for 4 days.After the fourth day, both cells were an opaque white, and the currenthad increased to 280 uA. The reaction was stopped. Both cells wereemptied, and the products were cleaned with acid.

The reaction appeared to have occurred as predicted. It is unclear ifany zinc metal was deposited onto the zinc rod. The calcium cell islikely white from calcium oxide and excess calcium chloride. Severallarge pieces of carbon were formed in the reaction. Some of the piecesappear to be very flat, similar to the graphene produced from earlierreactions. The stainless steel electrode appeared to be unchanged fromthe reaction. Previous reactions caused significant corrosion on thelow-quality stainless steel.

The sample was removed from the calcium cell and filtered in aglass-fiber filter. Then, the sample was placed in 1M HCl until bubblingof acetylene ceased. The sample was filtered again. Then the sample wasplaced in concentrated HCl and stirred for approximately 1 minute. Thesample was filtered again on a glass-fiber filter. Next, alcohol (amixture of methyl and ethyl alcohol) was washed over the sample on thefilter. Approximately 200 mL of alcohol was used. The sample was rinsedwith this alcohol 10 times. Finally, the sample, on the filter, wasplaced in a drying oven (80° C.) for one hour. The sample was thenanalyzed under the SEM and using Ramen spectroscopy.

The product of the elemental carbon material reaction product is furthershown in FIGS. 46-51 which are described more below.

FIG. 46 is a first SEM image showing the carbon product in Example 6with use of a potentiostat, Sample D (scale bar 10 microns). There areat least two interesting aspects of FIG. 46. The first is that it showsa fin or projection of elemental carbon material that appears to beroughly 90° or perpendicular from the surfaces it is attached to. Thesecond aspect is that the fin or projection seems to be very thin in thethird dimension in relation to the other two dimensions.

FIG. 47 is an SEM image showing the carbon product in Example 6 with useof a potentiostat, Sample D (scale bar 5 microns). FIG. 47 shows tieredgraphene hexagons with increasing particle size.

FIG. 48 is an SEM image showing the carbon product in Example 6 with useof a potentiostat, Sample D (scale bar 50 microns). The most interestingthing about FIG. 48 is the different characteristics of the elementalcarbon material at different points on the particle. FIG. 48 appears tobe one solid particle of elemental carbon. On the left hand side towardsthe top it has a textured appearance with material projecting from thesurface. On the right-hand side of the particle appears to be moresmooth on the surface. This represents the possibility of producingelemental carbon with different characteristics in the same particle.

FIG. 49 has two SEM images showing the carbon product in Example 6 withuse of a potentiostat, Sample D (scale bar 50 and 10 microns). The imageon the left (A) is a two dimensional particle of elemental carbon orgraphene. The image on the right (B) shows a magnified portion showingthe depth or third dimension of the particle. It appears to have fouralternating layers that appear to run in different directions. Thisfigure also represents the possibility of producing particles ofelemental carbon with different characteristics and orientations.

FIG. 50 has two SEM images showing the carbon product in Example 6 withuse of a potentiostat, Sample D (scale bar 20 microns, A, and 10microns, B). The most interesting thing about FIG. 46 is the thicknessor depth in the third dimension. FIG. 50 shows elemental carbon materialthat appears to be very thin in the third dimension relative to thefirst two dimensions. This elemental carbon also represents thepossibility of producing three-dimensional structures of elementalcarbon that is mostly “empty space”.

FIG. 51 is an SEM image showing the carbon product in Example 6 with useof a potentiostat, Sample D (scale bar 10 microns). FIG. 51 shows apiece of elemental carbon that is sp3 hybridized. It has very distinctlydifferent characteristics than the three-dimensional stacks ofgraphene-like material.

FIG. 52 shows an image of the bulk material produced in Example 6.Although there is still a high percentage of amorphous looking carbon,the amount of crystalline carbon is much higher than anything seen inthe prior thermal reactions (U.S. application Ser. No. 14/213,533 andPCT Application PCT/US2014/028755). This is roughly the same amount ofmaterial observed in the previous examples. However, the crystalstructure was different. There are more well-defined and varying shapesincluding two dimensional sheets or plates of elemental carbon. Thefibrous material seen on the right side of the image is contaminationfrom the filter used during the separation and purification operations.

FIG. 53 shows a magnified image of the elemental carbon crystallinematerial seen in the upper right-hand quarter of FIG. 52. Note thewell-defined two-dimensional layers of this material.

FIG. 54 provides a further magnified image of FIG. 53 at a scale 10 μm.This more clearly shows the stacked two dimensional structure of thematerial.

FIG. 55 provides an image of a large composite piece of elemental carbonat a scale of 100 μm. This three-dimensional structure is a composite ofsmaller two dimensional plate-like pieces of elemental carbon. Thismaterial represents a very high surface area three-dimensional material.

FIG. 56 provides a magnified image of FIG. 55. Note how the twodimensional elemental carbon pieces form the structure.

FIG. 57 shows the Raman spectra at seven different sites taken from asample of the material produced in Example 6.

Example 7

The apparatus was for an ethanol electrochemical reaction withpotentiostat, single CaC2 crystal.

A Zn/ZnCl₂∥CaC₂/CaCl₂ was set up using saturated salts on both sides indry ethanol. The zinc is in the form of a zinc rod. A single CaC₂crystal was put in the CaCl₂ cell. The Ag/AgCl₂ reference cell wasplaced in the zinc cell. The potentiostat and an ammeter were connectedin series between the zinc and CaC₂ electrodes.

The objectives were to continue with gather information and data toimprove the operation of the electrolysis reaction system, and producecarbon material.

The reaction that was expected to occur was:CaC₂+ZnCl₂→2C+CaCl₂+Zn  (1)

In this reaction, Zn⁺² is reduced to elemental zinc. The carbide anionis oxidized to elemental carbon. The standard reduction potential ofeither half-cell is not known in ethanol. It has been observed that thisreaction occurs spontaneously at room temperature.

With an applied potential of 0V, a current of 150 uA was measured. Thisis the highest galvanic current measured thus far. When a voltage wasapplied, the current did not change until a voltage of 2.20V. Then, thecurrent decreased rapidly and changed sign to −150 uA at 2.50V.

The current steadily increased to approximately 1000 uA. The zinc cellappeared to be clear, having consumed the zinc chloride, presumably.More zinc chloride was added. The current increased to 1500 uA. The cellquickly cleared again, and again, more zinc chloride was added. Thecurrent increased to 1800 uA. The cell was left overnight.

The next day, the current had reached 2,300 uA. The piece was removed.The bottom of the piece had noticeable black layer on it. Upon theaddition of acid in methanol, the black pieces fell off. There was nonoticeable acetylene smell until the acid mixture was added.

The material was filtered after sitting in HCl over several days. Largepieces were still visible.

Example 8

The main objective for Example 8, was to react aluminum carbide toproduce elemental carbon using the potentiostat to apply a forcedexternal voltage. Nearly the same apparatus and the same experimentalprocedure as Example 6 were used. The changes made were to accommodatethe aluminum carbide which is in the form of −325 mesh fine particlesize power. The aluminum carbide used was: Sigma-Aldrich; AluminumCarbide; Powder, −325 mesh, 99%; Product number: 241837; CAS: 1299-86-1.

The changes to the apparatus are made to the carbide cell and the anodewhich held the carbide. First, the tea ball strainer was replaced with aplatinum basket supporting a platinum crucible to hold the smallparticle size, powder like aluminum carbide. The platinum holderreplaced the stainless steel holder to eliminate any surface effectsbetween the holder and the carbide. Normally the calcium carbide isplaced in the platinum mesh basket. But with the small particle size ofthe aluminum carbide, the mesh platinum basket supported a solidcrucible which held the aluminum carbide. A smaller diameter hole wasdrilled in a new rubber stopper acting as a cap for the carbide cell. Aplatinum wire was fed tightly through the opening in a loop wasfabricated on the end of the wire inside of the cell. The basket, whichhad a holding rod attached with a hook, was connected to the platinumwire exiting the carbide cell. The platinum wire would then be connectedto the potentiostat and amp meter. It had been observed in previousexperiments that no vapor was being produced which needed to be ventedfrom the carbide cell. Therefore, there was no longer need for thebubbler or the hollow tube exiting the cell to vent any vapors formed.

The reaction that is expected to occur is:Al₄C₃+6ZnCl₂→3C+4AlCl₃+6ZnIn this reaction, Zn⁺² is reduced to elemental zinc. The carbide anionis oxidized to elemental carbon. The standard reduction potential ofeither half-cell is not known in ethanol. It has been observed that thisreaction occurs spontaneously at room temperature. CaCl₂ was added tothe aluminum cell to provide conductivity and available chloride anions.

A forced external voltage of 1.0 V was applied. Initially, a current of580 uA was measured. The current steadily increases from this value. Allof the excess ZnCl₂ dissolved or was consumed within a few minutes. Thealuminum cell appears opaque white. Eventually, a clear layer formed onthe bottom of the aluminum cell. It should be noted, since Al₄C₃ is afine powder, so no agitation was used in the aluminum cell, as it wouldcause the carbide to come out of the crucible.

Products of reaction were subjected to the same cleaning andpurification operations as Example 6 with one exception. Due to theproblem with contamination, the fiber filter was replaced with a silverfilter. The silver filter provided the same high flow rate efficiencybut was much more structurally solid and did not contaminate the samplesproduced. One note with the aluminum carbide reaction is that lesselemental carbon was recovered due to the stoichiometry of the chemicalreaction. Because less was recovered, the analysis was performed on thesample collected on the filter. Therefore, an accurate weight for thisexperiment could not be determined. An estimate for the recovery wouldbe roughly one tenth of a gram. The sample was analyzed using the SEMand Ramen spectroscopy.

FIG. 58 is an SEM image of the bulk sample produced from Example 8. Itappears that a high percentage of the material produced was amorphouscarbon with a smaller percentage of crystalline carbon like the thermalreactions (U.S. application Ser. No. 14/213,533 and PCT ApplicationPCT/US2014/028755). It did appear that a slightly larger amount of thematerial was crystalline as opposed to amorphous as produced in thethermal reactions. However, this is unclear because the aluminum carbidewas in the form of −325 mesh powder.

FIG. 59 is an image of the crystalline material produced in Example 8.The two things of note are the piece of curved two dimensional materialand the shape, structure, and overall appearance of the other piece ofelemental carbon. This SEM images unique in that two pieces of elementalcarbon with characteristics that have not yet been observed are seenside by side.

FIG. 60 is the Raman spectra of the products produced by Example 8. Thispicture shows evidence of the standard sp2 carbon peaks. Also, towardsthe left side of the spectrum, there are additional peaks that are notwell defined. These peaks may indicate additional forms of carbon, butcould also be contaminants or undesired products of reaction that werenot removed and the separation and purification operations or simplycontaminates in the carbide. The separation and purification operationswere difficult in this experiment due to the small particle size of thealuminum carbide used as a reactant.

Example 9

The main objective for Example 9 was to perform an experiment where thestandard carbide cell including calcium carbide immersed in a solutionof ethanol and calcium chloride was reacted with a cathode of elementaltin immersed in a solution of ethanol and stannous chloride. The secondobjective of this experiment was to apply a forced external voltage tothis reaction system using the potentiostat.

The same apparatus and procedure was used for Example 9 as was used inExample 8 with three differences. The first difference is that theelemental zinc cathode immersed in a solution of ethanol and zincchloride was replaced with an elemental tin cathode immersed in asolution of ethanol and stannous chloride. The second was that Example 9used calcium carbide instead of aluminum carbide. The third was in theplatinum carbide holder used as part of the anode in the particle sizeof the carbide. The carbide holder was altered simply by removing thesolid crucible from the mesh basket. The mesh basket includes a meshopen top cylinder roughly ¾ of an inch in diameter and 2 inches high.One solid piece of calcium carbide roughly 2 cm was placed inside theholder.

The reaction that is expected to occur is:CaC₂+SnCl₂→2C+CaCl₂+SnIn this reaction, Sn+2 is reduced to elemental tin. The carbide anion isoxidized to elemental carbon. The standard reduction potential of eitherhalf-cell is not known in ethanol. It has been observed that thisreaction occurs spontaneously at room temperature. CaCl2 was added tothe aluminum cell to provide conductivity and available chloride anions.

A forced external voltage of 1.0 V was applied. Initially, a current of5100 uA was measured. The current steadily increases from this value.All of the excess ZnCl₂ dissolved or was consumed within a few minutes.This current stayed constant for approximately 5 hours, then steadilyrose to 8000 uA.

At the conclusion of the reaction, the products of the calcium cell werefiltered on a silver membrane filter, then treated with HCl. The productappears to be a black powder.

FIG. 61 shows an SEM image of elemental carbon produced in Example 9.The carbon appears to have a stacked nature similar to that of thehexagonal shapes sheets. However it is different in that it is notconsistent and seems to be “bunched up”.

FIG. 62 shows an SEM image of the carbon bent at an acute angle. This isa unique image in that it shows the material on edge. In thisorientation, you can clearly see the nature of the angle of thematerial.

FIG. 63 represents the Raman spectra for the material produced inExample 9.

Example 10

Example 10 represents an experiment performed using an updated design ofa newly fabricated small bench scale glass reaction apparatus. The newreactor can be seen in FIG. 18. There were several improvements andchanges made to the new reactor. The main purpose for the new reactordesign was to accommodate an ion exchange membrane used in place of theglass fritted filter from the reactor in FIG. 17. The ion exchangemembrane not only prevents solid materials from migrating between thecells, it does not permit mass transfer at all. It is also selectivewith respect to charge of the ions that are capable of passing throughthe membrane. For instance, one membrane will permit cations frompassing through and not permit anions from passing. Another membranewill permit anions and resist cations from passing through.

Since the ion exchange membrane will need to be replaced whereas theglass fitted filter did not, the reactor was designed as two piecesconnected with a clamp and sealed together with an O-ring gasket andvacuum grease. This connection was made in the salt bridge where the ionexchange membrane can be replaced and altered between experiments. Alsoin the salt bridge was a larger stopcock to accommodate the largerdiameter of the salt bridge and permit greater migration of ions fromone cell to the other. A further design change of the new reactor isthat the diameter of the two cells was increased several centimeters tofacilitate better agitation from the stirring bar and accommodate awider range of anodes and cathodes for future testing.

The final change of the reactor design was to add additional ports toeach cell on the opposite side of the connection to the salt bridge.These ports enter the cell at a 45° angle and can be sealed using aglass plug due to the glass ground joint. These ports are to accommodatereference electrodes or to allow access to the cell or any futurereactions.

The reaction performed was the standard Zn/ZnCl₂∥CaC₂/CaCl₂ was set upusing saturated salts on both sides in dry ethanol. The zinc is in theform of a zinc rod. The zinc rod was submerged into saturated zincchloride in ethanol along with a Ag/AgCl₂ reference electrode. CaC₂ isavailable as a single large piece (about 2 cm). It was placed in aplatinum crucible that was placed in the platinum cage. The cage is usedto provide support for the crucible. The cage and crucible weresubmerged in a solution of CaCl₂ in ethanol. The potentiostat was hookedup with the data acquisition system. A voltage of 1.0 V was applied. Thereaction that is expected to occur is:CaC₂+ZnCl₂→2C+CaCl₂+ZnIn this reaction, Zn⁺² is reduced to elemental zinc. The carbide anionis oxidized to elemental carbon. The standard reduction potential ofeither half-cell is not known in ethanol. It has been observed that thisreaction occurs spontaneously at room temperature. CaCl₂ was added tothe calcium carbide cell to provide conductivity and available chlorideanions.

After being allowed to run for four several days, the calcium pieceturned opaque white and appeared to form layers. When the piece wasplaced in acid, some black pieces fell off of the larger white mass, andthe white mass appeared to be unaffected by the acid. However, aftersetting in the acid for 30 minutes, the piece eventually dissolved. Verylittle black material remained.

By the end of the reaction, the calcium cell was a clear yellow color.The zinc cell was a translucent white. The zinc growth on the rod wasconsiderable, and visible through the solution with a flashlight. Theion exchange membrane gained a brownish color on the calcium side and ablack color on the zinc side. The black color, however, was not presentat the point of liquid contact. It was above the level of the liquid.

FIG. 64 shows an SEM image at a scale of 200 μm of the products ofreaction from Example 10 or the first reaction using an exchangemembrane with the updated reactor. The material has an appearancesimilar to that of the amorphous carbon. However, as will be seen in thenext several figures, this material appears to be crystalline with anappearance of the surface of the material being “chewed up”.

FIG. 65 shows a magnified image of the material seen in FIG. 64 at ascale of 30 μm. This more clearly shows that the material is crystallineelemental carbon and not the amorphous elemental carbon.

FIG. 66 shows an even more magnified image of the material seen in FIGS.65 and 66 at a scale of 10 μm. It is clear from this image that thematerial is crystalline and not the amorphous carbon.

FIG. 67 shows the Ramen spectra from the analysis of the products ofExample 10.

Example 11: Reaction of Calcium Carbide with Zinc Chloride in Methanol

The organic solvent reaction was a relatively simple reaction used toshow that the calcium carbide was conductive and would react at roomtemperature in a solution of a solvent and dissolved metallic salt.

The experiment was prepared in the controlled argon atmosphere of theglove box. 300 mL of dried methanol was placed in a standard 500 mLErlenmeyer flask. 100 g of zinc chloride was also added to theErlenmeyer flask. A magnetic stir bar was also placed in the flask and arubber stopper was fitted to seal it. Calcium carbide was crushed to acoarse particle size of roughly less than 1 cm. The calcium carbide wasthen added to the flask and the rubber stopper placed on it to seal. Thesealed flask now contained 20 g of calcium carbide, 300 mL of driedmethanol, 100 g of zinc chloride, and a magnetic stir bar.

The sealed flask was removed from the glove box and placed on a stirplate. The reaction was allowed to proceed for three days. It was thenstopped and removed from the stir plate. The flask was opened and thecontents subjected to the standard separation and purificationoperations. There was very little product remaining after the cleaningand separation procedure. This was expected due to the conductivity ofcalcium carbide and the expected low rate of reaction. There was enoughmaterial to be analyzed under the SEM and with Ramen spectroscopy.

FIG. 68 shows an image of an elemental carbon material that appears tobe two dimensional and very thin. This is evident from the fact that theelectron beam can “see” through the material.

FIG. 69 shows a very consistent stack of elemental carbon hexagonalsheets with a cross-sectional area of roughly 20 cm. This hexagonalstack is sitting on top of a larger piece of what appears to be stackedtwo dimensional elemental carbon.

FIG. 70 shows a second well-defined stack of hexagonal sheets oftwo-dimensional carbon. This image, along with FIG. 69, shows that thisreaction is possible at room temperature and atmospheric pressure.

FIG. 71 shows the Raman analysis from a sample of the products ofExample 11. This further shows that it is possible to produce elementalcarbon at room temperature via this reaction technology.

Example 12

Example 12 describes small particle size graphene exfoliation in theultrasonic bath with a low sonication energy.

A small portion (about 0.1 g) of the cleaned products were placed inglass centrifuge tubes which were then filled with NMP. The centrifugetube was then immersed a lower power ultrasonic bath (Cole-Parmer Model:8854). The graphene in NMP was sonicated for four hours and then removedfrom the bath.

The tubes were then centrifuged and examined. The NMP in the tubes withthe smaller particle size sample had exfoliated graphene that remainedin solution. INSTRUMENTATION: The following instruments were used forthe working examples: Hitachi S-4700 Scanning Electron Microscope and aRenishaw InVia Raman Microscope.

What is claimed:
 1. A method comprising: producing elemental carbonmaterial from the oxidation of carbide in at least one carbide chemicalcompound in at least one anode of an electrochemical cell apparatus,wherein the electrochemical cell apparatus is a galvanic cell apparatus,and wherein the elemental carbon material is produced at a reactionpressure of about 0.1 torr to about 5 atmospheres.
 2. The method ofclaim 1, wherein the carbide chemical compound is a salt-like carbide oran intermediate transition metal carbide.
 3. The method of claim 1,wherein the carbide chemical compound is a salt-like carbide.
 4. Themethod of claim 1, wherein the carbide chemical compound is a methanide,an acetylide, or a sesquicarbide.
 5. The method of claim 1, wherein thecarbide chemical compound is calcium carbide, aluminum carbide, sodiumcarbide, magnesium carbide, lithium carbide, beryllium carbide, ironcarbide, copper carbide, and chromium carbide.
 6. The method of claim 1,wherein the carbide chemical compound is calcium carbide or aluminumcarbide.
 7. The method of claim 1, wherein the carbide chemical compoundhas sufficient electronic conductivity to function as an anode.
 8. Themethod of claim 1, wherein the carbide chemical compound has anelectronic conductivity of at least 10⁻⁸ S/cm.
 9. The method of claim 1,wherein the electrochemical cell apparatus further comprises at leastone cathode.
 10. The method of claim 1, wherein the electrochemical cellapparatus further comprises at least one cathode which is a metalcathode.
 11. The method of claim 1, wherein the electrochemical cellapparatus further comprises at least one metal cathode, wherein thecathode is a zinc, tin, iron, copper, or silver cathode.
 12. The methodof claim 1, wherein the electrochemical cell apparatus further comprisesat least one metal cathode, wherein the cathode is a zinc or tincathode.
 13. The method of claim 1, wherein the electrochemical cellapparatus anode is contacted with at least one first solution comprisingat least one solvent and at least one salt and the electrochemical cellapparatus further comprises at least one cathode which is also contactedwith at least one solution comprising at least one solvent and at leastone salt.
 14. The method of claim 1, wherein the electrochemical cellapparatus further comprises at least one salt bridge.
 15. The method ofclaim 1, wherein the electrochemical cell apparatus further comprises atleast one ion exchange membrane.
 16. The method of claim 1, wherein areaction temperature for producing the elemental carbon material isabout 10° C. to about 90° C.
 17. The method of claim 1, wherein areaction temperature for producing the elemental carbon material isabout 15° C. to about 50° C.
 18. The method of claim 1, wherein areaction temperature for producing the elemental carbon material isabout room temperature.
 19. The method of claim 1, wherein the reactionpressure for producing the elemental carbon material is about 0.9atmosphere to about 1.1 atmosphere.
 20. The method of claim 1, whereinthe reaction pressure for producing the elemental carbon material isabout 720 torr to about 800 torr.
 21. The method of claim 1, wherein theelemental carbon material is produced at about 15° C. to about 50° C.and about 720 torr to about 800 torr.
 22. The method of claim 1, whereinthe production of elemental carbon material is carried out without useof an external voltage source.
 23. The method of claim 1, wherein theelectrochemical cell apparatus comprises an external voltage source toregulate the oxidation reaction.
 24. The method of claim 1, wherein theproduction of elemental carbon material is carried out with use of anexternal voltage source to regulate the oxidation reaction.
 25. Themethod of claim 1, wherein the production of carbon is carried out withuse of an external voltage source to regulate the oxidation reaction,and an external voltage is used at a particular voltage to enhanceproduction of one elemental carbon material product over other differentelemental carbon material products.
 26. The method of claim 1, whereinthe elemental carbon material is more than 50% sp2 carbon.
 27. Themethod of claim 1, wherein the elemental carbon material is more than50% sp3 carbon.
 28. The method of claim 1, wherein the elemental carbonmaterial is more than 90% carbon.
 29. The method of claim 1, wherein theelemental carbon material comprises two-dimensional plate-likestructures.
 30. The method of claim 1, wherein the elemental carbonmaterial comprises two-dimensional plate-like structures stacked on topof one another.
 31. The method of claim 1, wherein the elemental carbonmaterial comprises at least some three-dimensional structures.
 32. Themethod of claim 1, wherein the elemental carbon material comprises atleast one piece which has a lateral dimension of at least one mm. 33.The method of claim 1, wherein the elemental carbon material issubjected to at least one purification step.
 34. The method of claim 1,wherein the elemental carbon material is treated with acid and water.35. The method of claim 1, wherein the elemental carbon material issubjected to at least one step which produces particles of the elementalcarbon material.
 36. The method of claim 1, wherein the elemental carbonmaterial is subjected to at least one exfoliation step to producegraphene.
 37. The method of claim 1, wherein the galvanic cell apparatusproduces electrical power to power at least one load which is anotherelectrochemical cell.
 38. The method of claim 1, wherein the carbidechemical compound is calcium carbide or aluminum carbide, wherein thegalvanic cell apparatus anode is contacted with a solution comprising atleast one organic solvent and at least one dissolved salt, and thegalvanic cell apparatus cathode is also contacted with a solutioncomprising at least one organic solvent and at least one dissolved salt,and wherein the elemental carbon material is produced at about 15° C. toabout 50° C. and about 720 torr to about 800 torr.
 39. The method ofclaim 1, wherein the carbide chemical compound is in the form ofindividual pieces or particles.
 40. The method of claim 1, wherein thecarbide chemical compound is in the form of individual pieces orparticles having a size of less than one cm.
 41. The method of claim 1,wherein the carbide chemical compound contacts at least one electricallyconductive material.
 42. The method of claim 1, wherein the carbidechemical compound is held in an electrically conductive container. 43.The method of claim 1, wherein the apparatus further comprises at leastone solution comprising at least one solvent and at least one dissolvedsalt, and the solution is free of dissolved carbide chemical compound.44. An electrochemical cell apparatus for carrying out the method ofclaim
 1. 45. The method of claim 1, wherein the anode is an anodeelectrode structure comprising the at least one carbide chemicalcompound, wherein optionally the carbide chemical compound is asalt-like carbide; and at least one electronically conductive structuralelement different from the carbide chemical compound and contacting theat least one carbide chemical compound.
 46. The method of claim 45,wherein the electronically conductive structural element is a metal. 47.The method of claim 45, wherein the electronically conductive structuralelement is a non-metal.
 48. The method of claim 45, wherein theelectronically conductive structural element is graphite.
 49. The methodof claim 45, wherein the electronically conductive structural element isa non-metallic container and the carbide chemical compound is held inthe non-metallic container.
 50. The method of claim 45, wherein theelectronically conductive structural element is a graphite container andthe carbide chemical compound is held in the graphite container.
 51. Themethod of claim 45, wherein the electronically conductive structuralelement is a basket and the carbide chemical compound is held in thebasket.
 52. The method of claim 45, wherein the electronicallyconductive structural element is a graphite basket and the carbidechemical compound is held in the graphite basket.
 53. The method ofclaim 1, wherein the carbide chemical compound is in the form ofindividual pieces or particles having a size of at least one micron. 54.The method of claim 1, wherein the carbide chemical compound is dividedinto separate portions which are each contacted with at least oneelectrically conductive structural element.
 55. The method of claim 1,wherein the carbide chemical compound is at least about 95% pure. 56.The method of claim 1, wherein the elemental carbon material comprisessp1 carbon.
 57. The method of claim 1, wherein the elemental carbonmaterial is subjected to at least one exfoliation step.
 58. The methodof claim 1, wherein the elemental carbon material is subjected to atleast one doping step.
 59. The method of claim 1, wherein the carbidechemical compound is calcium carbide.